Accepted Manuscript

Title: First row transition metal complexes of

di-o-substituted-diarylamine-based ligands (including
carbazoles, acridines and dibenzoazepines)

Author: Stuart J. Malthus Scott A. Cameron Sally Brooker

PII: S0010-8545(15)30145-4
DOI: http://dx.doi.org/doi:10.1016/j.ccr.2016.02.006
Reference: CCR 112200

To appear in: Coordination Chemistry Reviews

Received date: 27-12-2015

Revised date: 14-2-2016
Accepted date: 14-2-2016

Please cite this article as: S.J. Malthus, S.A. Cameron, S. Brooker, First row
transition metal complexes of di-o-substituted-diarylamine-based ligands (including
carbazoles, acridines and dibenzoazepines), Coordination Chemistry Reviews (2016),
http://dx.doi.org/10.1016/j.ccr.2016.02.006

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Highlights:

- concise survey of design, synthesis and properties of 385 complexes of di-ortho-

substituted-diarylamine-based ligands (including carbazoles, acridines and
dibenzoazepines)
- tables summarising selected features of the 96 structurally characterised complexes
- summary of activities of the complexes, which range from biocidal (medicinal,

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agricultural), through magnetic, electronic and optical, to catalytic (especially
polymerisations)
- accessible, attractive and useful reference work for those working in this rapidly

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expanding area

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First row transition metal complexes of di-o-substituted-diarylamine-based

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ligands (including carbazoles, acridines and dibenzoazepines)
Stuart J. Malthus,† Scott A. Cameron†‡ and Sally Brooker*
Department of Chemistry and the MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Otago,
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PO Box 56, Dunedin 9054, New Zealand

Contents
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1. Introduction and scope

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2. Review of examples of the ten structural motifs

2.1 Motif A – Simple substituted diarylamines
2.2 Motif B – Triarylamines
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2.3 Motif C – Acyclic iminomethyl or oxazole substituted diarylamines

2.4 Motif D – Macrocyclic diarylamine based systems
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2.5 Motif E – Acyclic and macrocyclic bis(diarylamine) based systems

2.6 Motif F – Acyclic carbazole based systems
2.7 Motif G – Macrocyclic carbazole based systems
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2.8 Motif H – Extended porphyrins

2.9 Motif I – Acridines and phenoxazines
2.10 Motif J – Dibenzoazepines
3. Structural comparisons
4. Concluding remarks
5. References

Keywords: Tolylamine ligands; 3d transition metal ions; carbazole; bisphenylamine; imines; macrocycles; structure;
catalysis; biological activity; magnetism; fluorescence

ABSTRACT

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First row transition metal (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) complexes of di-o-substituted-
diarylamine-based ligands reported prior to April 2014 (identified by SciFinder® Scholar) are reviewed.
Only the 408 complexes where the 3d metal ion is coordinated to the central nitrogen donor atom of this
fragment are considered. The ligands identified using this search feature o-substituted aryl groups and
include those based on diarylamines, triarylamines, carbazoles, acridines, phenoxazines and
dibenzoazepines. The vast majority of the ligands employed are noncyclic, but approximately 40 of the
complexes feature macrocyclic ligands. The ligand and metal complex syntheses, as well as the structures
of the 96 complexes so characterised, are described. The complexes present a wide range of interesting
properties which are also summarised here, including biocidal, magnetic, optical and catalytic activity, the

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last of these being the most commonly explored.

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† joint first authors
‡ present address: Department of Biochemistry, Albert Einstein College of Medicine, 1300 Morris Park Ave, Bronx,
NY 10461, United States

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1. Introduction and Scope
First-row transition-metal complexes of substituted
di-o-tolylamine-based ligands are reviewed. The
literature was surveyed in April 2014 using a
SciFinder® Scholar sub-structure search for the
fragment shown in Figure 1, featuring any first row
transition metal ion (Ti to Zn) coordinated to the
nitrogen donor atom of the di-o-tolylamine
fragment, and yielded 408 results. Of the 408
complexes, 385 were explicitly defined in the text of
the relevant document (the remainder were hidden
within patents or proposed to be generated in situ
prior to acting as catalysts), allowing inspection of
the synthesis, oxidation state, coordination sphere,
reactivity and other interesting factors. Therefore it
is these 385 compounds that are presented and
discussed in this review. Of these 385, 96 have been
structurally characterised (see later).
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Figure 1: The search fragment of interest; N-bound first-
row transition-metal (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu,
Zn) complexes of substituted di-o-tolylamine derivatives
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(use of any metal ion almost doubles the number of hits).
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This search fragment was chosen because (a) such
systems have important applications across many
fields, including interesting biocidal, magnetic,
optical and catalytic properties, which are outlined
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in this review, and (b) of its potential to form a wide
array of ligands providing a large variety of donor
environments, demonstrating the power of using this
relatively simple fragment and how subtle changes
to the resulting ligands can lead to new and
interesting results. This family of ligands and
complexes has not been reviewed before, but with
such a wide range of applications for the 385
complexes identified, and the control and tuneability
provided by using this moiety as a ligand platform,
we feel this review is timely and likely to generate
further interest in this class of compound.
The 385 complexes have been categorised into ten
basic structural motifs, A-I (Figure 2): simple
substituted diarylamines; triarylamines; acyclic
singly or doubly substituted diarylamines;
macrocyclic diarylamines; acyclic
bis(diarylamines); acyclic carbazoles; macrocyclic
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carbazoles; extended porphyrins; acridines and
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phenoxazines; and dibenzoazepines. Roughly half of
the complexes are of motif C ligands. Motifs E, A
and F are the next most common, whilst the
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remaining motifs (D, J, G, B, H and I) each
comprise only 3-20 examples. The vast majority of
the ligands are noncyclic, but approximately 40 of
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the complexes feature macrocyclic ligands (motifs
D, G and H).
These ten motifs fall into four general classes, those
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based on (i) di- or tri-arylamines (red box) being by
far the most common, with 83% of the complexes
falling into this category, (ii) carbazoles (blue box)
being the next most common, with 11% of the
complexes, whilst (iii) acridines or phenoxazines
(green box) and (iv) dibenzoazepines (black box)
together represent the last 6% of complexes (Figure
2).
The handful of ligands (3) belonging to motifs B
and J (R≠H) feature tertiary amine, NR3, type di- or
tri-phenylamine nitrogen atoms, so these coordinate
via a neutral sp3 nitrogen atom. Likewise, the
acridine and phenoxazole moieties in the handful of
motif I ligands coordinate via a neutral nitrogen
atom, however in this case it is a sp2 nitrogen atom
so it is also a π-acceptor.
In contrast, the N-atom in the search fragment in the
vast majority of the ligands, i.e. those belonging to
the remaining 7 motifs (A, C-H, Figure 2), is in the
form R2NH and in all but two cases[1, 2] is
deprotonated to R2N- before coordination. The bases
used include triethylamine, Na/KOH, Na/KOtBu,
and nBuLi, with the last of these typically requiring
stirring for up to 24 hrs. An exception to the use of
such bases is the use of the zinc(II) reagents ZnEt2
and Zn[N(SiMe3)2]2, where one of the anions acts as
the base removing the R2NH proton before
coordination of the zinc(II) ion.
In the following sections (Sections 2.1-2.10) each of
these ten motifs is presented in turn, with
consideration given to the synthesis of the ligands
Page 3 of 60
and complexes as well as to the structures and
properties (eg. biocidal, magnetic, optical and
catalytic) of the latter. A quarter (96) of the
complexes of interest have been characterised by
single crystal X-ray structure determinations. Half
of these feature ligands from motif C. There are 8-
14 examples for each of motifs E, D, F and B, only
1 example of each of motif A or H, and no examples
of these structures is presented in Section 3.
Selected X-ray crystal structures are pictured
throughout this review: hydrogen atoms, solvents of
crystallisation, counterions and disordered
fragments (if present) have been omitted for clarity.
These images were generated using POV-ray [3].

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of motifs I or J. A summary of the structural features

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Figure 2: The ten basic structural motifs (A → J) grouped into four general classes [ (red) di- or tri-arylamines,
(blue) carbazoles, (green) acridines or phenoxazines and (black) dibenzoazepines] observed in the 385 complexes
identified in the search defined in Figure 1.

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2. Review of Examples of the Ten Structural
Motifs
2.1 Motif A — Simple Substituted Diarylamines
This motif contains diarylamine ligands that are
substituted with (typically) non-coordinating
groups. This motif also considers diarylamines
where one of the phenyl rings is part of a fused
benzene ring system (phenanthralene or
naphthalene). Roughly one eighth of the 385
complexes feature ligands from this motif (Figures
3 and 4), but only one of these has been structurally
characterised (see later, Section 3). Many of the
articles relevant to this motif could not be accessed
(Russian or Chinese journals or patents), so, where
this is the case, only a brief summary of the work is
presented. These summaries were established from
the abstracts of these articles.
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Figure 3: Motif A: some simple substituted diarylamine-
based ligands: ligands H2La1 to HLa16.
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The copper(II) complexes of H2La1 with various co-
ligands, using sodium hydroxide as a base, were
investigated by Melnik and co-workers [4, 5]. The
complex [CuII(La1)2(OH2)], could be reacted further
with co-ligands to give compounds [CuII(La1)2(X)]
(where X = methyl-3-pyridylcarbamate or caffeine)
which exhibited d-d transitions at ca. 710 nm. EPR
values suggest these compounds exist in a dimeric
form such as [Cu2II(La1)4(X)2], with each copper
centre having a square-pyramidal coordination
environment. Reaction with other co-ligands gave
complexes of the form [CuII(La1)2(Y)2], (where
Y=3-pyridylcarbinol, nicotinamide, N,N-
diethylnicotinamide, 2,6-dimethanolpyridine or
nicotine). These compounds exhibited a d-d
transition at ca. 430 nm in the solid-state electronic
spectra, attributed to a tetrahedral coordination
geometry. The EPR spectra were said to indicate
the compounds have an octahedral geometry with
varying degrees of tetragonal distortion.
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Konakhovich, Kriss and co-workers have
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investigated simple diarylamines (such as H2La1)
and their transition-metal complexes for a variety
of uses, such as agricultural and medical
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applications [6]. These ligands were investigated in
conjunction with mixtures of metal ions (FeIII–MnII,
FeIII–CoIII, or CuII–ZnII) for use as fertilisers to
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reduce the need for nitrates [7]. The metal
complexes of such ligands (H2La1) were also shown
to stimulate the germination and growth of lettuce
and oats at low concentration (0.0001–0.001%) and
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inhibit at higher concentrations (0.01%) [8, 9]. The
iron(III) complex stimulated root growth more than
the copper(II) complex, attributed to either the
higher lipophilicity or activity of iron(III).
Transition-metal complexes of H2La1 had low
toxicity when tested in mice (single oral
administration). The prophylactic activity of these
complexes was also investigated in mice orally
intoxicated with chloro-containing compounds
(lindane, DDT, polychlorocamphene and
polychloropine), of which the highest
detoxification activity was for lindane [6].
Copper(II) complexes of H2La1 and related
derivatives were also tested for in vitro and in vivo
activity in mice against Ehrlich adenocarcinoma
and lymphadenosis NK/Ly. In vitro, all complexes
showed greater cytotoxic activity than the anti-
cancer drug ThioTEPA [10]. In vivo,
intraperitoneal administration of the complexes
gave better therapeutic results than did
subcutaneous treatment.
The copper(II) complexes of H2La1 (and other
closely related biologically active phenylanthranilic
acid derivatives) have been studied in detail, using
EPR in particular. Strongly pH-dependent dimer
formation is observed [11]. Paramagnetic 1:1 and
1:2 complexes formed in 80% aqueous dioxane at
higher pH. At lower temperatures the EPR signal
intensity drops, consistent with the formation of the
dimeric complex [12]. Stability constants of the
monomeric complexes and dimerisation constants
Page 6 of 60
were determined. Magnetic properties also indicate
complexes are dimeric [49]. The degree and
kinetics of dimerisation of copper(II) complexes of
such ligands was also investigated in 80% dioxane
or 90% DMF [13].
The incorporation of these copper(II) complexes
into the hydrophobic polymer poly(methyl
(by several times) the biocidal activity of the
ligands. Mohan and co-workers have investigated
the transition-metal complexes of H3La2 in a search
for better non-steroidal anti-inflammatory drugs
(NSAIDs) [19]. Such drugs typically have high
incidences of gastric ulceration and other side
effects related to the kidney, liver, bone marrow
and skin. The transition metal ions have various

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siloxane) was investigated by IR and ESR roles in healing and some are known to suppress

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spectroscopy [14]. The complex was less strongly inflammation and have anti-ulcer properties. The
bound to the polymer than the precursor copper(II) cobalt(II), nickel(II), copper(II) and zinc(II)
material. It was asserted that this polymer bound complexes were synthesised and found to have

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material is able to absorb toxic substances octahedral coordination geometries with three
(excreted by diseased cells) and has useful water molecules coordinated. The peaks observed
“controlled-release” properties in conjunction with in the electronic spectra of these complexes are

suitable solvents. These complexes were also
investigated for their ability to catalyse the
oxidation of ascorbic acid and degradation of H2O2
[12]. The 1:1 (metal : ligand) complexes were more
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summarised, along with the assignments, in Table
1. The anti-inflammatory activity of these
complexes was investigated, with the zinc complex
being the most active. A raft of other anti-

active than 1:2 complexes.
The corrosion-preventive properties of H2La1 (and
analogues) and the ability of these compounds to
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form complexes (Fe, Zn, Cu) was investigated [15].
The effect of hydrophobic ring substitution and the
oxidation of these compounds was also probed.
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Sungur and co-workers have developed and
optimised an indirect AAS method to quantify
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inflammatory and analgesic tests were carried out
on this zinc compound, establishing it as being
comparable to ibuprofen and naproxen, although at
higher dose rates. Notably, this complex has a low
incidence of gastric irritation (a common problem
for NSAIDs).
Table 1: UV-vis transitions and assignments for the
copper(II), nickel(II) and cobalt(II) complexes of H3La2.
Transition

levels of the analgesic-inflammatory drugs (H2La1 Metal (nm) Assignment

2
and similar compounds) in commercial tablet Cu 793 Eg → 3T2g
3
formulations [16]. To achieve this the analyte of Ni 385 A2g → 3T1g (P)
3
A2g → 3T1g (F)
p

interest is dissolved and reacted with 4.5 580

3
equivalents of [Cu(NH3)4]SO4 (at pH 10), extracted 980 A2g → 3T2g (F)
4
T1g → 4T1g (P)
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into CHCl3, re-extracted into 0.3 N nitric acid Co 500

4
solution and finally analysed by atomic absorbance 560 T1g → 4A2g (F)
4
(at 324.7 nm using an acetylene-air flame). Linear 1350 T1g → 4T2g (F)
relationships between the drug concentrations and
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atomic absorption values were established. The
tablets were also analysed using an HPLC method,
wherein there was no significant difference
between the mean values and precisions of the two
methods (at the 95% confidence level).
The 1:1 and 1:2 (homo- and hetero-leptic)
copper(II) complexes of H3La2 (and related
analogues) were prepared and characterised by
Sharma and co-workers [17, 18]. The ligands and
metal complexes were screened for their
antibacterial (Staphylococcus and E. coli) and
antifungal (A. niger and A. nidulens) activity [18].
In some cases, coordination with copper increased
In 1958, Sweet and co-workers reported the acidity
constants of H3La2 (and related analogues) in 1:1
water:dioxane [20]. Two pKa values were
identified: 6.05 for H3La2 → [H2La2 ]–, and 7.02 for
[H2La2]– → [HLa2 ]2–. The stability constants of the
1:1 metal complexes (CoII, CuII, NiII, ZnII) with this
ligand were also determined (Table 2).
Table 2: Logarithms of stability constants of 1:1 metal
complexes of ligand H3La2 in 1:1 water:dioxane at 35°C.
cobalt(II) nickel(II) copper(II) zinc(II)
5.1 5.4 8.0 5.6

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Seminara and co-workers investigated the effect of
copper(II) coordination by altering ligand
aromaticity, number of chelate rings and ligand
flexibility [21]. The ligand H3La2 and co-ligand
(2,2’-dipyridyl = dipy; 1,10-phenanthroline = phen;
or 2,2’,2”-terpyridyl = terpy) were reacted with
NaOH and copper(II) perchlorate, resulting in
neutral complexes, [CuII(HLa2 )(co-ligand)], which
were insoluble in water and common organic
solvents. The asymmetric and symmetric IR
stretching frequencies for the carboxylate groups
occur at 1570–1620 and 1370–1400 cm−1
respectively, attributed to bridging bidentate
carboxylate group. These insoluble compounds
were assigned a tetragonally-distorted octahedral
geometry in the solid state based on the reflectance
spectra, and had values of 15.15 and 14.71 kK for
the complexes with dipy and phen co-ligands
respectively.
Isayev and co-workers prepared the nitro-
substituted ligands H2La3–a9 (Figure 3), some
prepared using a solid phase modified Ullmann
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reaction. A variety of copper(II) and zinc(II)
complexes were also synthesised by reaction with
the sodium or potassium salts of the appropriate
ligand. These compounds are reported to have anti-
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inflammatory, analgesic, neuroleptic, cholagogic
(promotes the flow of bile) and bacteriostatic
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activity, and are considered to be slightly toxic by
intraperitoneal or intragastric administration [22,
23]. The copper(II) complexes of HLa10, HLa11,
HLa12 and HLa13 were synthesised, via the sodium
p
salt, by Isayev and co-workers. As only the abstract
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of the article was available, the metal : ligand ratio
in these complexes is unknown, but they fall into a
“low toxicity” classification when orally
administered, and possess anti-inflammatory,
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choleretic, bacteriostatic and antifungal properties
[24].
Trogler and co-workers investigated a series of 19-
electron complexes based on cyclopentadienyl-
cobalt, using tetra-azabutadiene ligands [25]. The
compound derived from HLa14, [CoIII(Cp)(HLa14)],
was used for comparison purposes in the
electrochemical studies. A one electron reversible
reduction process occurs at −1.35 V (in MeCN
versus NHE), having a peak separation of ca. 150
mV. An irreversible oxidation process occurs at
EPA 0.40 V, with subsequent reduction events at
EPC 0.31 and 0.07 V observed on the return scan.
Boyle and co-workers found that neutral nickel
complexes of HLa15 (Figure 3) were highly active
ethylene polymerisation catalysts [26, 27]. The
ligand was prepared by reaction of lithiated 1,3,5-
triisopropylbenzene in THF with ZnCl2 under
nitrogen at 0 °C. The resulting organozinc
compound was reacted with anthranil at RT for 3
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days. The crude product was purified by column
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chromatography through silica in 9:1 PE : Et2O, to
yield yellow crystals of HLa15 (32%). The
structurally characterised four-coordinate square
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planar nickel(II) complex, [NiII(La15)(PPh3)(2-
tolyl)], deprotonating using potassium hydride, was
tested for its ethylene polymerisation activity by
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reaction in an autoclave. Toluene was degassed
with ethylene, after which the nickel compound (50
mmol) and Ni(COD)2 activator (2 eq.) were added
and the chamber pressurised with ethylene for 24
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hrs. The highest activity, of 30 kg.mol−1.hr−1, was
observed at 200 psi (highest pressure tested). The
resulting polymer under these conditions had a
molecular weight of 24,000 g.mol−1 (determined by
1 13
H– and C–NMR analysis in 1,2,4-
trichlorobenzene / benzene-d6 at 120°C).
Alternative Lewis acid activators B(C6F5)3 and
MAO were also investigated but were found to
completely inhibit the polymerisation activity.
In 2012 Severin and co-workers reported a
vanadium(III) complex of HLa15[28]. The HLa15
ligand was obtained, as the vanadium(III) complex,
by thermal rearrangement of the initial product of
the reaction of the N-heterocyclic carbene 1,3-
dimesityl-imidazol-2-ylidine with nitrous oxide
(N2O) and [VIII(Mes)3(THF)]. This showed that the
vanadium complex activated N2O, resulting in
cleavage of both the N-O bond and N-N bond
consecutively.
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Figure 4: Motif A: benzene fused (phenanthrene and
naphthalene) diarylamine-based ligands: ligands La17 to
H2La20.
The ligand La17 was synthesised by condensing
phenanthrenequinone with 2,6-di-isopropylaniline
by refluxing in MeOH with 1–2 drops of formic
acid for 24 hrs [29]. After cooling, the green
crystals were isolated and recrystallised from
M
heptane (85%). This ligand can undergo single
electron reduction to give a radical anion. The deep
green nickel(II) complex of the radical anions,
[NiII(La17)], was also prepared.
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Li and co-workers investigated the nickel(II)
complexes of La19 and La20 for use as ethylene
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polymerisation catalysts [30]. Ligand La19 was
prepared by Schiff-base condensation of 9,10-
phenanthrene-quinone with 2,6-dimethylaniline in
p
the presence of TiCl4 and DABCO in toluene at
140°C for 24 hrs. The crude ligand could be
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purified by column chromatography through silica
in 8:1 hexane:EtOAc, followed by recrystallisation
from hexane, giving a deep-red crystalline solid in
50% yield. Ligand La20 was prepared in an
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analogous manner, except the reaction was carried
out in chlorobenzene at over 160 °C. Following
purification an orange solid was isolated in 35%
yield. The complexes [La19NiIIBr] and [La20NiIIBr]
were prepared and were tested for their catalytic
activity in the polymerisation of ethylene. For these
tests, MAO, ethylene and catalyst in DCM and
toluene were reacted for 60 min, quenched and
precipitated with acidified MeOH. These catalysts
exhibit high ethylene polymerisation activity in the
presence of MAO, reaching up to 22.8 × 105 g.(mol
Ni)−1.hr−1 (at −15 °C with 0.5 µmol of catalyst and
3000 eq. of MAO) for the former; and 6.9 × 105
g.(mol Ni)−1.hr−1 (at 0 °C with 1 µmol of catalyst
and 3000 eq. of MAO) for the latter. The latter
catalyst, [La20NiIIBr], produces polyethylenes with
lower molecular weight and a greater extent of
branching. Notably, the former catalyst,
[La19NiIIBr], when used at lower polymerisation
temperatures (−15 °C), produces polyethylene with
ultra-high molecular weights (1.26–2.14 × 106
g.mol−1), indicating this ligand system provides a
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greater steric demand on the axial faces of the
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nickel centre than related catalytic systems (2,3-
butanedione and acenaphthene-quinone).
Importantly, these systems can be activated by
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relatively small amounts of MAO (Al/Ni = 50),
which was attributed to the moisture and polar
group tolerance of these nickel complexes.
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2.2 Motif B — Triarylamines
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There is only one ligand present in Motif B,
2,2’,2”-nitrilotribenzoic acid (Figure 5). Only ten
of the 385 complexes used this ligand, eight of
which are structurally characterised (see later,
Section 3). Due to resonance of the lone pair of the
tertiary nitrogen atom in this ligand with the three
phenyl groups, the nitrogen atom is not tetrahedral
but instead tends towards trigonal-planar and has
low basicity. Consequently, this tertiary amine is a
poor donor for metal ions, so does not always
coordinate. However, the three carboxylic acid
substituents on the phenyl rings provide a
trigonally arranged set of oxygen donors, with the
tertiary amine at the apex, making this an effective
O3-tri- or NO3-tetra-dentate ligand (see later, Figure
6) – with or without binding of the central tertiary
amine donor.
Figure 5: Motif B: the 2,2’,2”-nitrilotribenzoic acid
ligand, H3Lb1, is the only example in this motif.
Krämer and co-workers investigated H3Lb1 for (a)
promoting the formation of transition metal clusters
that are well suited for applications such as
SMMs[31] and (b) the unique
“on/intermediate/off” coordination of the tertiary
Page 9 of 60
amine donor to transition metal ions in response to
various stimuli, in particular the redox state of the
metal ion[32], but also to changes of pH or solvent
or the presence of co-ligands. The M—NTPA ranges
defined by these authors are: “on” 2.0–2.4 Å;
“intermediate” 2.4–2.6 Å; and “off ” >3 Å. This
type of reversible interaction is interesting because
such behaviour is associated with supramolecular
applications, for example:
“molecular shuttles and motors, chirality switches,
interconversion of allogones or ‘molecular
machines’ based on metal-ion translocations
between ligand compartments.” (Krämer and co-
workers [32]).
There are also iron enzymes that feature such
on/off coordination of a histidine nitrogen in the
course of the catalytic cycle, namely diiron
peroxidase and soybean lipoxygenase [33, 34].
Ligand Synthesis
The synthesis of H3Lb1 involves an Ullmann
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reaction of methyl anthranilate with methyl 2-iodo-
benzoate in the presence of copper bronze, 18-
crown-6 and K2CO3 in o-dichlorobenzene at reflux
under argon for 17 hrs [35]. The solvent was
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removed from the resulting mixture and then
filtered through Celite with hot EtOH. The crude
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product could be purified by column
chromatography through silica in 3:1
hexane:EtOAc (55%). The resulting trimethyl ester
p
was hydrolysed to the triacid by reaction with
NaOH in 1:1 EtOH:water. This mixture was
ce
refluxed for 3 hrs and the precipitate resulting from
neutralisation (using dilute HCl) collected (93%).
The synthesis of this ligand had also been reported
earlier, by Hellwinkel and Melan [36].
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Metal Complexes
This ligand, H3Lb1, was reacted with a variety of
transition metal ions (in water, acetonitrile, or
methanol, and Ca(OH)2, NaOH or NEt3). Many of
the resulting complexes have an overall negative
charge, as all three carboxylic acid groups are
deprotonated in all cases. The complexes are either
mononuclear with a protonated base as the counter
cation (NHEt+), or are di- or hexa-nuclear with a
hydrated metal salt as the cation (Figure 6). These
eight compounds were crystallised; the
composition, M—NTPA bond distance and crystal
colours can be seen in Table 3 [21, 25, 37-39].
Table 3: The composition, M—NTPA bond distance and
crystal colours of various complexes of H3Lb1.
Composition M-NTPA (Å) Colour
X = HNEt3+
[NiII6(Lb1)4(OH)2(OH2)2]X2 2.199-2.247 green
[CuII(Lb1)]2X2 2.092 orange
[NiII(Lb1)]2X3ClO4 2.164-2.177 orange
[FeII(Lb1)]2X2 2.430 orange
t
([FeIII(Lb1)]2O)X2 2.562 orange
X = H2O
ip
[CuII(Lb1)X]6[CuIIX4]3 2.056-2.096 blue-green
[CoII(Lb1)OH][CoIIX6] 2.261 purple
[ZnII(Lb1)OH]6[ZnIIX6] 2.327 colourless
cr
In the mono- and di-nuclear compounds, all except
the iron(III) complex had trigonal-bipyramidal
us
coordination environments, whereby the three
carboxylate oxygen donors occupied the equatorial
positions, the amine donor one of the axial sites and
the other axial site was occupied by an oxygen
an
donor (section 3, later). This oxygen donor was
either from water or from a bridging carboxylate or
oxo moiety. Specifically, for the mononuclear
copper(II), nickel(II), cobalt(II) (Figure 6 top) and
zinc(II) complexes the oxygen donor was from a
molecule of water. In the dinuclear copper(II)
(Figure 6 middle), cobalt(II) and iron(II) complexes
this was a bridging carboxylate oxygen atom. In the
dinuclear iron(III) complex this was a bridging oxo.
Preparation of an iron(III) complex of this ligand in
water with NaOH results in an octahedral complex
that is not coordinated to the amine, but to three
carboxylate oxygen donor atoms and three
molecules of water. In the hexanuclear nickel(II)
complex the nickel ions were all in octahedral
environments, being bridged by the carboxylate
groups, water molecules and/or hydroxide ions. In
the UV-vis spectrum, the intensity of a ligand-
based band associated with the nitrogen
conjugation, at about 300 nm, decreases
significantly upon complexation with metal(II)
perchlorates. This was attributed to the change in
geometry at this nitrogen atom, affecting the extent
of conjugation. The intensity of the band decreases
by 16% (MnII), 24% (FeII), 35% (ZnII), 49% (NiII),
58% (CoII) and 73% (CuII), in accordance with
decreasing M—NTPA distance in the solid state
(Table 3). This effect was not observed for the
iron(III) complex, indicating the iron ion is not
coordinated to the amine. A pH titration experiment
(monitored spectrophotometrically) was carried out
to investigate deprotonation of the complex
[Zn(Lb1)(OH2)]– in MeOH/H2O using NaOH to
10
Page 10 of 60
give [Zn(Lb1)(OH)]2–. Deprotonation resulted in a
significant increase in the intensity of the 300 nm
band, attributed to a considerable weakening of the
Zn—NTPA bond. DFT calculations were carried out
to investigate these two species and supported this
suggestion.
M
d
te
p
ce
Ac
Figure 6: Crystal structures of (top) mononuclear
2[CoII(Lb1)(OH2)]•[CoII(OH2)6]•6H2O (Cambridge
Structural Database (CSD) refcode HAHKOR),[69]
(middle) dinuclear [CuII2(Lb1)2]•2NHEt3•2MeCN (CSD
refcode HAHKAD)[69] and (bottom) hexanuclear
[NiII6(Lb1)4(OH)2(OH2)2]•2NHEt3•5MeCN•2.6H2O (CSD
refcode FEHGEF)[68] complexes derived from H3Lb1,
redrawn from data obtained from the Cambridge
Crystallographic Data Centre (CCDC) as published in the
respective references. Carbon = Light grey, Oxygen =
Red, Nitrogen = Light Blue, Cobalt = Navy Blue, Copper
= Orange and Nickel = Green.
The hexanuclear nickel(II) complex (Figure 6
bottom), with a dicubane-like core [NiII6(Lb1)
(µ 3−OH)2(µ−OH2)]2- was shown to have pre-
dominantly ferromagnetic interactions, with
interesting behaviour at low temperature attributed
to the population of low energy, high spin
multiplicity states [31].
The dinuclear iron complex (NHEt3)2[Lb1FeII]2 was
investigated for use as an oxidation catalyst [38].
This compound efficiently catalyses the oxidation
t
of hydroquinone to benzoquinone in conjunction
ip
with H2O2 in 1:1 MeOH : water at pH 7. This
catalyst was found to have an initial turnover rate
of 13 min−1.
cr
2.3 Motif C — Acyclic Iminomethyl or Oxazole
Substituted Diarylamines
us
Motif C is again a simple acyclic diarylamine
structure. However, here one or both of the aryl
rings is substituted at the 2-position by either an
an
iminomethyl or oxazole based group (Figure 7). If
only one such group is present then the other ring
features an alkyl substituent. A total of 74 ligands
have been employed in this motif to date. In all
cases except one, the ligand is deprotonated only at
the amine of the diarylamine unit, producing mono-
anionic N2-donor bidentate or dianionic N3-donor
tridentate ligands. In all cases these acyclic imine
and oxazole ligands are synthesised metal-free,
then deprotonated using a strong base (eg. nBuLi)
and finally complexed with the desired transition
metal ion. Roughly half of the 385 complexes in
this review feature ligands from this motif. More
than half of the structurally characterised
complexes, specifically 51 out of 96, feature this
motif.
Figure 7: Motif C: The diarylamine unit is flanked on
one or both side(s) by either: an oxazole/thiazole unit; a
phenyl substituted imine; or an alkylamino imine. If only
11
Page 11 of 60
one such group is present then the other ring features an
alkyl substituent. See later, Figures 8, 10, 13, 15, 20 and
21, for the details of the 74 such ligands reported to date.
Monoanionic bidentate nitrogen containing ligands,
including some that feature this motif, have been
developed for complexation with main group and
transition metal ions. Such complexes have been
investigated for their catalytic/initiator properties in
ring-opening polymerisation (ROP), for instance
complexes incorporating ligands derived from β-
diketimates. In particular, the synthesis of poly(ɛ-
caprolactone), which has recently been attracting
attention
“due to its potential applications in medicine,
pharmaceuticals, and tissue engineering such as
delivery media for the controlled release of drugs,
scaffolds, and the delivery of antibodies and genes
”. (Ye et al. [40])
Ligand Synthesis
The diarylamine derivatives (HLc1 and HLc2, Figure
8) were synthesised by amination of 2-(2-
M
bromophenyl)-4,4-dimethyl-2-oxazoline with
substituted anilines [41]. 2,4,6-Trimethylaniline
was coupled using a copper(I) catalyst (CuI) in
DMSO at 110°C with ɛ-proline and K3PO4 for 24
hours, whereas 2,6-di-isopropylaniline was coupled
d
using Pd(OAc)2 in refluxing toluene with DPEPhos
and NaOtBu for 2–3 days. The ligands were
te
purified by column chromatography or
recrystallisation in moderate to good yields (65%
and 70% respectively). Ligands HLc3-6 and HLc7,8
p
where synthesised by the Du group using a
Buchwald-Hartwig amination using a palladium
ce
based catalysis and BINAP [42, 43]. All of the
ligands were synthesised in moderate to low yields
(~40%).
Ac
Figure 8: Motif C: In the singly oxazole substituted
subset, the other phenyl ring in the diarylamine unit is
multiply substituted, giving ligands HLc1 to HLc9.
Metal Complexes
The monometallic complexes [LZnIIEt] (where L =
Lc1 or Lc2) and dimetallic complex [Lc2ZnII(OBn)]2
were prepared using diethylzinc(II) as the base and
source of zinc(II). The structurally characterised
dimetallic complex, [Lc2ZnII(OBn)]2 (Figure 9,
Section 3), features two tetrahedral zinc(II) ions in
an N2O2-donor coordination environment. It was
tested for its catalyst/initiator properties for ROP of
t
cyclic esters. Initial tests at room temperature found
ip
this compound performed best using toluene as the
solvent. The typical procedure was as follows:
toluene was added to a flask containing varying
cr
quantities of monomer [ɛ-lactide (LLA) or ɛ-
caprolactone (CL)] and catalyst under nitrogen.
The reaction mixture was stirred at 50 °C for a
us
given time, before being quenched with acetic acid
and the polymer precipitated by addition of n-
heptane. The crude products were recrystallised
from THF/hexane and dried under vacuum. This
an
compound was an efficient initiator for the
polymerisation of LLA. Much lower activity was
observed for the polymerisation of CL. In both
cases the polymerisation process was shown to
have both “living” and “immortal” characters.
Figure 9: Crystal structure of [Lc2ZnII(OBn)] 2 (CSD
refcode TIMLIL), redrawn from data obtained from the
CCDC as published in reference [41]. Carbon = Light
Grey, Oxygen = Red, Nitrogen = Light Blue and Zinc =
Pink
Optically active molecules are important in
pharmaceutical and materials industries, and can be
prepared using a range of methods, including
asymmetric catalysis. Chiral ligands are important
in asymmetric catalysis of organic reactions.
Tridentate C2-symmetric N,N,N-type ligands
bearing chiral oxazoline or thiazoline units (Figure
10) have been used for this purpose in a number of
asymmetric catalytic reactions such as Nozaki–
Hiyama allylation, Henry, Friedel–Crafts, ketone
12
Page 12 of 60
hydro-silylation, cyclopropanation and nitroalkane
Michael addition reactions. Use of first-row
transition metal ions in catalysts, compared to the
heavier metal ions, is desirable as these have less
impact on the environment. Six such complexes
have been structurally characterised (Section 3),
but many more have been made and studied in situ.
Several monometallic nickel complexes
[(Lc3-6)NiII(PPh3)] were prepared by the Du
group[43]. The typical procedure for each complex
synthesis was addition of nBuLi to a solution of
ligand in THF, stirred for 1 hr, volatiles then
removed and the residue dissolved in toluene and
added to a toluene solution of NiCl(Ph)(PPh3)2. X-
ray quality crystals of each of these complexes
were obtained. The structure determinations show
the nickel(II) centre is coordinated to a methyl
carbon, the anionic amine nitrogen and the oxazole
nitrogen in a pincer fashion, with the remaining
coordination site on the nickel ion occupied by a
triphenylphosphine (Section 3). These chiral
asymmetric CNN pincer nickel complexes showed
M
sp3 C–H bonds may be activated, warranting
further investigation of the nature of the C–H bond
activation and its potential in asymmetric catalysis.
d
Subsequently, in 2013, Du and co-workers used the
same series of ligands, HLc3-8 (Figure 8), to prepare
te
a family of zinc(II) complexes[42]. In general, the
ligand was added to Zn[N(SiMe3)2]2 in toluene,
stirred for approximately 8 hrs, then taken to
p
dryness in vacuo, giving the respective complexes
[(Lc3-15)ZnN(SiMe3)2] in high yields (>90 %).
ce
Several of these complexes have been structurally
characterised, showing an N3 mononuclear binding
environment (see Section 3). All of these
complexes showed appreciable activity in the
Ac
copolymerisation of CO2 and CHO (CHO =
cyclohexane oxide), with complexes containing one
chiral centre on the oxazoline ring and a large
bulky substituent bound to the amine nitrogen (e.g.
2,6-diphenyl) giving the best activity and
selectivity as catalysts.
Ligand Synthesis
Ligands HLc10-14 (Figure 10) were prepared as
follows[1, 44]. Reaction of 2,2’-dicarboxyl
diphenylamine with SOCl2 at reflux for 4 hrs,
followed by removal of solvent, yields the diacyl
chloride, which is reacted with the amino alcohol
of choice, with TEA in DCM at RT for 24 hrs. This
crude intermediate could be purified by column
chromatography through silica in EtOAc to give
the bis(hydroxyamide) precursors (i-Pr, i-Bu, Ph,
Bn, t-Bu substituted) as pale yellow solids in very
good yields (74–92%). The bis(hydroxyamide)
precursors were reacted with mesyl chloride and
TEA in DCM for 20 hrs. The resulting bismesylate
compound was reacted with aqueous NaOH and
t
MeOH at reflux for 3 hrs. Finally these oxazole
ip
based ligands could be purified by column
chromatography through silica in 10:1 PE : EtOAc,
to give HLc10 (94%), HLc11 (81%), HLc12 (68%) and
cr
HLc13 (72%) as pale yellow solids or oils and HLc14
(72%) and HLc15 (71%) as white solids. An almost
identical synthesis was also employed in a patent
us
publication by Yianyun He and coworkers, giving
ligands HLc15-19 as well as some other previously
described ligands[45].
an
Figure 10: Diarylamine unit wherein each phenyl ring is
singly substituted by an oxazole derivative, giving
ligands HLc10 to HLc34.
The analogous bis(thiazoline) ligands, HLc20-c24
(Figure 10), were prepared by reaction of the
bis(hydroxy-amide) intermediates with P2S5 in
pyridine at reflux for 22 hrs, followed by
purification by column chromatography through
silica using 20:1 PE : EtOAc, to give HLc20 (54%),
HLc21 (47%), HLc22 (47%), HLc23 (82%) and HLc24
(57%) as pale yellow solids.
A series of ten asymmetric ligands (HLc25-34, Figure
10) where one pendant arm contained a thiazole
group and the other an oxazole group, with a
variety of –R groups, were synthesised by Guiry
and co-workers in 2011[46]. The synthesis of all of
these ligands was achieved through a microwave
assisted Hartwig-Buchwald aryl amination, in a
wide range of yields (from 22-79%). The general
procedure was as follows. Under an atmosphere of
nitrogen the desired bromophenyl-thiazole and
13
Page 13 of 60
aminophenyl-oxazole were added to sodium tert-
butoxide, DPPF, Pd2(dba)3 and dry toluene. The
tube was then sealed and microwaved at 180 °C for
1 hr. After removal of solvent in vacuo the pure
product was isolated by preparative thin layer
chromatography using cyclohexane:EtOAc, 8:1.
Metal Complexes
Copper(II) triflate complexes of HLc10-c15 and
HLc20-c24, excluding HLc14, were generated in situ
when doing catalyst studies (see below), using
trimethylamine as the base. The UV-vis spectra of
the copper(II) triflate complexes of HLc12 and HLc22
and the free ligands were investigated. Compared
to the respective ligands, the complex
[Lc24CuII(OTf)] exhibited additional peaks at 320
and 435 nm (ca. 6000 and 9500 L.mol−1.cm−1
respectively), whereas the complex [Lc22CuII(OTf)]
exhibited an additional peak at 467 nm (ca. 7750
L.mol−1.cm−1). Asymmetric catalysis of the Henry
reaction was carried out using the chiral ligands
HLc10-15 and HLc20-23 (excluding HLc14), in a ‘one-
pot’ combination with Cu(OTf), TEA, MeNO2 and
M
an α-keto ester (ethyl pyruvate or ethyl
trifluoropyruvate) [44]. This mixture was stirred for
16 hrs under nitrogen and the products purified by
column chromatography through silica in 3:1
d
PE:EtOAc. A number of different bases were
attempted (pyridine, NMO, Hünig’s base), but were
te
no better than TEA. The conversion and
enantioselectivity were dependent on the base to
catalyst ratio. The highest enantioselectivity was
p
achieved when using alkyl halides as solvent
(CHCl3, ClCH2CH2Cl and CH2Cl2), but the highest
ce
yields were obtained in neat reactions. Conversion
of ethyl trifluoropyruvate was normally lower and
resulted in products with lower ee’s. Notably, use
of the bis(thiazoline) ligands gave slightly better
Ac
enantioselectivities than the bis(oxazoline) ligands.
The iron(II) acetate and cobalt(II) acetate
complexes of HLc10–c14 (Figure 10) were also
generated in situ, when doing catalyst studies (for
hydrosilylation and conjugate reduction reactions,
see below). The iron(II) and cobalt(II) chloride
complexes of HLc10 were prepared separately and
showed no catalytic activity. Both complexes were
crystallised, but the former was intentionally
exposed to air, thereby producing the iron(III)
complex, [Lc10FeIIICl2] (Figure 11, see later Section
3). This iron(III) complex is C2 symmetric and
features an N3Cl2-donor set.
t
ip
cr
us
Figure 11: Crystal structure of [Lc10FeIIICl2] (CSD
refcode GUTTOF), redrawn from data obtained from the
CCDC as published in reference [1]. Carbon = Light
grey, Oxygen = Red, Nitrogen = Light Blue, Chloride =
an
Green and Iron = Orange.
Nishiyama and co-workers have investigated iron
and cobalt catalysed hydrosilylation of ketones and
cobalt catalysed conjugate reduction of enones [1].
In a typical hydrosilylation reaction, the ketone of
interest was reacted with (EtO)2MeSiH in the
presence of ligand (HLc10-14) and either iron(II)
acetate or cobalt(II) acetate in THF at 65 °C for 24
hrs. The resulting product is hydrolysed using
TBAF and KF in MeOH and water at 0 °C, and
then purified by column chromatography through
silica in EtOAc/hexane. For instance, conversion of
4-acetylbiphenyl to the corresponding alcohol
using either iron(II) acetate or cobalt(II) acetate
complexes of HLc10-14 was achieved in excellent
yield (90–99%) and varying ee’s (20–94%).
Notably, two equivalents of silane were required
for high yields, with use of 1.2 eq decreasing the
yield to just 57%. Other hydrosilanes (PhMe2SiH,
Ph2MeSiH, Ph2SiH2) did not promote
hydrosilylation. Nickel(II) and copper(II) acetate
did not exhibit catalytic behaviour. The highest
enantioselectivities for the reduction of ketones
were obtained using the HLc13-Fe(OAc)2 (ee 73%)
and HLc12-Co(OAc)2 (ee 94%) catalyst systems,
and so these were investigated further using 17
different ketones. The HLc12-Co(OAc)2 system
showed generally higher yields (95–99%) and
enantioselectivities (only four had ee’s lower than
90%) compared to the HLc13-Fe(OAc)2 system,
which still had good yields (88–99%), but
consistently lower ee’s (50–88%). In a typical
asymmetric conjugate reduction reaction, the β,β-
14
Page 14 of 60
disubstituted enone of interest was reacted using
the same reaction conditions as above, with ligands
HLc10-14, except only Co(OAc)2 was used. The
resulting product was hydrolysed with aqueous HCl
in THF and MeOH at 0 °C. Use of ligand HLc11
gave the best yields (90–93%) and
enantioselectivities (ee 65–75%). The ee values
obtained were greatly dependent on the substituents
present in the enone substrate.
Nishiyama’s group further investigated the
hydrosilylation of 4-acetylbiphenyl, catalysed by
the [Lc10FeIIICl2] system, which has been
structurally characterised (see later, Section 3).
This trigonal-bipyramidal iron(III) complex has no
catalytic activity by itself. Supplementing the
reaction with additives gave some interesting
results [47]. Addition of copper or manganese
powder, ZnCl2 or silver salts resulted in no
reaction. In contrast, addition of NaOAc, NaOtBu
or Mg resulted in excellent conversion (97, 99 and
92% respectively), but only modest ee values (57,
55 and 15% respectively). Notably, these last three
M
additives, in conjunction with the [Lc10FeIIICl2]
catalyst, gave an excess of the R enantiomer. In
contrast, addition of zinc powder and reaction for
48 hrs resulted in excellent conversion (97%) to the
d
product, but now with an excess of the S
enantiomer (ee 41%). Addition of one equivalent of
te
zinc powder and additional HLc10 ligand results in
no reaction. The hydro-silylation was also tested
with zinc powder added to [Lc13FeIIICl2] (98% yield
and ee 65% S) and [Lc12FeIIICl2] (67% yield and ee
p
21% S). Other hydrosilanes were tested and had
ce
similar yields (92–99%) and ee’s (65–71%), with
the absolute configurations remaining constant
throughout. These were (EtO)2MeSiH, (EtO)3SiH,
Ph3SiH, Ph2SiH2. Notably, using Ph2MeSiH did not
Ac
result in any conversion. Considering the success
using the [Lc13FeIIICl2] / Zn powder catalyst system,
a large number of ketones were tested and
compared against the HLc13-Fe(OAc)2 catalyst
system. In all but 3 of the 18 reactions inversion of
the stereochemistry was observed. The UV-vis
spectra and magnetic moment (by Evans method)
were investigated before and after addition of zinc
powder to [Lc10FeIIICl2]. A broad peak at 631 nm
disappears and a new peak at 432 nm appears.
Also, the effective magnetic moment changes from
5.9 µ B to 4.8 µ B, attributed to reduction by zinc
from high-spin iron(III) to high-spin iron(II).
Klein’s group showed that the nickel complex of
HLc10 ([Lc10Ni(R)], where R = CF3, CH3, Cl) could
be used to generate radical, R·, through a one-
electron oxidation process[48]. The evidence for
this process was established using N-tert-butyl-α-
phenylnitrone as a spin trap. The reaction was also
monitored by UV-vis-near-IR absorption
spectroelectrochemistry and EPR. DFT calculations
t
on the ground and oxidised states were also
ip
calculated.
Nakada’s group synthesised a pair of iron
cr
complexes containing ligand HLc12 and HLf3 (see
section on Motif F later), [(Lc12,f3)Fe(Cl)2] for use
as catalysts in the asymmetric epoxidation reactions
us
[49]. However, the iron complex of HLc12 showed
no catalytic activity and therefore it is not fully
discussed. Rather, the paper focuses on the iron
complex of HLf3, which will be discussed later in
an
this review as it is an example of motif F (Section
2.6).
Jianyun He and coworkers[45] developed a series
of bis(oxazoline) ligands, HLc16-19, which were
complexed with a variety of scandium compounds
to give complexes of form [(Lc16-19)Sc(X)n], where
X = CH2SiMe3, CH(SiMe3)2, CH2-(2,6-iPr2-C6H3),
CH2CH=CH2, MeCH=CHCH2, CH2=CPhCH2,
CH2=CMeCH2, CH2C6H4NMe2-o, CH2C6H4OMe-o
or Cl and n = number of co-ligands coordinated. As
this was a patent publication the abstract elaborates
no further than to say that the title catalyst showed
high activity for the polymerisation of isoprene and
1,3-butadiene and the preparation of (S)-3-indolyl-
3-benzyl alcohol or pyrimidoindolone.
Introduction of fluorine into organic molecules may
bring about many changes, such as chemical and
metabolic stability, enhanced lipophilicity,
conformational changes, and changes in polarity
[50, 51]. Fluorinated compounds have growing
importance in agrichemical, pharmaceutical, and
materials industries [50, 52]. The introduction of
trifluoromethyl groups into organic halides,
catalysed by metal complexes, is desirable but not
well established. For this reason Vicic and co-
workers have carried out some fundamental studies
to understand perfluoroalkyl manipulations at a
metal centre [50].
The complexes [Lc10NiIIX] (where X = Cl, Me, CF,
Ph) and [Lc10NiII(THF)](OAc) were prepared
15
Page 15 of 60
(Figure 10), and all three of the organometallic
complexes, plus two of the coordination
complexes, were structurally characterised (Figure
12, see later Section 3). In all five structures the
nickel(II) centres are square-planar (diamagnetic)
and thus NMR characterisation was carried out for
all of them. There is a peak at −29.9 ppm in the
19
F−NMR of [Lc10NiII(CF3)]. The redox behaviour
of these complexes is strongly dependent on the co-
ligand. The methyl, trifluoromethyl and chloride
coordinated complexes all exhibit irreversible
oxidation processes at −0.17, 0.42 and 0.55 V
respectively (vs. Fc/Fc+ in THF). Notably, the
methyl complex also exhibits a further process at
higher potentials, attributed to the rapid cleavage of
the co-ligand and formation of a THF-coordinated
adduct. This finding was supported by comparison
of the cyclic voltammograms and UV-vis spectra
with that of the [Lc10NiII(THF)](OAc) complex.
M
d
te
Figure 12: Crystal structure of [Lc10NiIICF3], redrawn
p
from data obtained from the article ESI as published in
reference [50]. Carbon = Light grey, Oxygen = Red,
ce
Nitrogen = Light Blue, Nickel = Green and Fluorine =
Yellow
Guiry and co-workers generated in situ a series of
Ac
zinc catalysts for enantioselective Friedel-Crafts
reactions and chromium catalysts for Nozaki-
Hiyama-Kishi allylation of benzaldehyde[46]. The
zinc catalysts were generated by addition of
Zn(OTf)2 to the selected ligand (HLc25-34) under an
atmosphere of nitrogen in dry toluene and stirred
for 30 minutes. The resulting solution was used to
react trans-β-nitro-styrene with indole. The
chromium catalysts were generated by addition of
chromium(III) chloride and manganese to a
Schlenk tube under an atmosphere of nitrogen
followed by dry toluene and try THF; this
suspension was stirred for 1 hr. DIPEA and the
desired ligand (Lc25-34) were dissolved in dry THF
and stirred for 1 hr. These two solutions were then
mixed with allyl bromide. This solution was then
used to carry out the Nozaki-Hiyama-Kishi
allylation of benzaldehyde. Both series of zinc and
chromium complexes proved effective in catalysing
their respective reactions and inducing
enantioselectivity. It is proposed that these ligands
could be used to facilitate a range of other
t
asymmetric metal catalysed transformations.
ip
Biodegradable, biocompatible and permeable
(co)polymers derived from ε-caprolactone or
cr
lactide have been widely used in medical fields and
there is ongoing interest in the development of new
(ring opening) polymerisation catalysts. The groups
us
of Lin [53], Ko [54] and Parkin [55] have
investigated ligands HLc35, HLc36 and HLc37
respectively, as potential components of such
polymerisation catalysts. The ligands feature the
an
same core diphenylamine unit but have differing
pendant arms (Figure 13), which have the potential
to coordinate to the metal centre and increase the
steric demand, producing a single active site.
Subtle changes to the periphery of catalysts can
result in dramatic enhancements of catalytic
activity or selectivity, so the effect of variation of
the NR2 pendant arm is of considerable interest.
Figure 13: Motif C: The diarylamine unit is substituted
at the 2-position on one phenyl ring only, by an
alkylamino imine unit, giving ligands HLc35 to HLc40.
Ligand Synthesis
The potentially tridentate ligands HLc35 and HLc37
(Figure 13) were prepared in two steps [53, 55].
The first is the Schiff base condensation of 2-
fluorobenzaldehyde with N,N-dimethylethylene-
diamine or N,N-diisopropylethylene-diamine in
hexane at RT for 12 hrs. The second step is the
amination of this 2-fluoro-aryl intermediate with
deprotonated/lithiated 2,6-di-isopropylaniline
(using nBuLi) in THF overnight. Ligand HLc35
could then be purified by column chromatography
through alumina (pre-treated with 1% TEA) in 8:1
hexane:EtOAc, yielding a yellow oil in 62% yield.
Ligand HLc37 was used in subsequent metal
complexation reactions as the lithium salt without
further purification. In contrast, the potentially
16
Page 16 of 60
tridentate ligand HLc36 was prepared with the steps
in the opposite order [54]. In order to do this, 2-
(2,6-di-isopropylphenylamino)-benzaldehyde was
prepared according to the literature [56].
Bromobenzaldehyde is first protected using
ethylene glycol in toluene with catalytic p-
toluenesulfonic acid for 16 hrs at reflux, using a
Dean-Stark trap (94% yield). This was then
coupled with 2,6-di-isopropylaniline using
Pd(OAc)2 , tri-tert-butylphosphine and NaOtBu in
THF at reflux for 16 hrs under nitrogen (78%
yield). The aldehyde functionality was returned by
deprotection using TFA in MeOH at RT for 1 hr
(94% yield). Finally, reaction of this aldehyde with
1-(2-amino-ethyl)piperidine and MgSO4 in hexane
at reflux for 12 hrs yielded the ligand HLc36 in 89%
yield. HLc36 could be recrystallised from Et2O [54].
The two ligands HLc38-39 (Figure 13) were
synthesised in analogous three step processes.[42,
57] The first step was the reaction of 2-
bromobenzaldehyde with anhydrous ethylene
glycol and p-toluenesulfonic acid. This mixture
M
was refluxed until a theoretical yield of water had
been collected in a Dean-Stark trap. The pure
product was isolated by washing the crude mixture
with 10% aqueous sodium hydroxide, water and
d
brine. The organic layer was then collected, dried
over MgSO4, filtered and solvent removed in
te
vacuo. This compound then coupled to 2,6-
dissopropylaniline using Pd(OAc)2, sodium tert-
butoxide and tri-tert-butylphosphine in dry THF
p
under a nitrogen atmosphere at reflux for 16 hrs.
The pure product, 2-(2,6-diisopropylphenyl-
ce
amino)benzaldehyde is then isolated by filtering the
reaction solution and extraction into ethyl acetate.
This organic solution was then washed with water
then dried over MgSO4 and the solvent removed
Ac
under vacuum. Finally this crude product is
dissolved in hexane, cooling to -20 °C overnight
caused the precipitation of the pure product. The
two ligands where then obtained by reaction of the
synthesised aldehyde with the desired amine in the
presence of anhydrous MgSO4.
Metal Complexes
The organometallic complexes [Lc35ZnIIEt] and
[Lc36ZnIIEt] were prepared and the latter complex
structurally characterised (see later, Section 3) [53,
54]. The zinc(II) ions are trigonal-planar, with just
two of the three possible N-donors bound, along
with the ethyl moiety, giving an N2C-donor set
overall. The catalyst properties of both complexes
for the polymerisation of various monomers were
investigated. In both cases, complexation resulted
in the disappearance of the NH proton resonance at
ca. 10.5 ppm. When testing the complex
[Lc35ZnIIEt], a solution of this catalyst (0.5 mol %),
ɛ-CL and BnOH in toluene was stirred at a given
temperature, during which the conversion yield was
t
monitored by 1H−NMR spectroscopy[83]. Once a
ip
suitable end-point had been reached the reaction
was quenched with water, precipitated with hexane,
filtered, redissolved in THF, again precipitated with
cr
hexane and then filtered and dried. The same
approach and catalyst loading was adopted for the
polymerisation of ɛ-LA, but that was concluded by
us
dissolving in DCM, followed by precipitation with
hexane.
This complex exhibits modest catalytic activity for
an
the ROP of ɛ-CL in the presence of BnOH in
toluene, wherein increased reaction temperatures
(50 °C) and times (3 hrs) were required to complete
the polymerisation. This complex exhibits good
activity for ROP of ɛ-LA in the presence of BnOH
in toluene, but requires prolonged reaction times
(4.5 hr) to achieve high conversion yields.
Similarly, tests of [Lc36ZnIIEt] involved addition of
β-butyrolactone (β-BL) to a rapidly stirred solution
of this catalyst (1 mol %) and 9-anthracene-
methanol (9-AnOH) in toluene [54]. This mixture
was then stirred at 55 °C for 4 hrs, before being
quenched by addition of water. The desired
polyhydroxybutyrate (PHB) polymer was
precipitated by addition of hexane. This product
was redissolved in DCM, then precipitated again
with hexane. Preparation of poly(ethylene glycol)
(PEG) and polycaprolactone (PCL) diblock co-
polymers with PHB, PEG-PHB and PHB-PCL, was
carried out in the same fashion except that after
reaction of the first monomer for a given time, the
second monomer was added and the reaction
continued. Specifically, poly(ethylene glycol)
methyl ether as initiator in conjunction with β-BL
to give PEG-PHB, or β-BL followed by ɛ-CL to
give PHB-PCL. The reactions were quenched in the
same manner. The average molecular weights (Mn)
for the resulting polymers were determined using
GPC (compared to polystyrene standards) and
analysis of 1H−NMR spectra. The polymerisation
of β-BL was achieved at 55 °C within 4 hrs,
whereby the resulting PHB polymer was produced
in excellent yield (90–99%) and narrow
17
Page 17 of 60
polydispersity (1.01–1.10), with the Mn linearly
proportional to the [β-BL] / [9-AnOH] ratio. The
polymers are capped with one 9-anthracenemethyl
ester and one hydroxyl chain end, indicating in situ
formation of metal 9-anthracenemethoxide active
species. This complex efficiently catalyses the ROP
of β-BL in a living and immortal fashion, but with
poor stereocontrol. Copolymerisation was readily
The zinc(II) centre in the monometallic [(Lc37)2Zn]
complex has a distorted tetrahedral N4-donor
environment provided by two bidentate (Lc37)–
ligands. Finally, in the dimetallic complex the two
zinc(II) centres are each in a regular (ω/90 = 1)
tetrahedral N2O2-donor environment, provided by a
ligand and two bridging hydroxide groups (Figure
14 bottom, see later Section 3).

t
achieved by sequential addition of differing

ip
monomers after given reaction times, with similarly
high reaction yields and narrow polydispersities.

cr
In two separate papers Ko’s group utilise the
similar ligands HLc38-39 to form zinc complexes
with a variety of ligand to metal ratios[57, 58].

us
They were synthesised for the purpose of acting as
catalysts in the ROP of cyclic esters and ɛ-CL, as
well as enabling the preparation of a PEG-b-PCL
copolymer. The ligand HLc39 formed the 1:1

an
complex [Lc39ZnEt], [Lc39Zn(DMAP)Et] and the
2:1 complex [Lc392Zn]. Synthesis of each of these
three complexes was controlled by the
stoichiometry of ZnEt2 : HLc39 and the reaction
M
solvent (either hexane, toluene or toluene/DMAP
respectively). Testing showed both [Lc39ZnEt] and
[Lc392Zn] were effective catalysts for ring opening
polymerisation of ɛ-CL in the presence of an
d
alcohol. [Lc39ZnEt] also allowed for the formation
of a PEG-b-PCL copolymer. Ko’s group[58], in
te

analogous conditions, synthesised [Lc38ZnEt],

[Lc38Zn(µ-OBn)]2 and [Lc382Zn]. The testing of
complexes [Lc38Zn(µ-OBn)]2 and [Lc382Zn] for their
p

ability to catalyse ɛ-CL and B-BL polymerisations

showed the former complex to be moderately
ce

effective for both polymerisations.

The crystal structure of the complex [Lc40ZnEt] was Figure 14: Crystal structures of complexes derived from
reported (see later, Section 3) in 2011 by Issa- HLc37 with (top) [Lc37ZnIIMe] featuring a coordinated
Ac

Madongo and Mu [59].
A range of zinc complexes derived from HLc37
were prepared, crystallised and their structural
parameters investigated [55]. This included
[Lc37ZnMe], [Lc37Zn(C6F5)], [(Lc37)2Zn], and
[Lc37Zn(µ−OH)]2, all of which were structurally
characterised (Figure 14, see later Section 3). In all
four cases only two of the three potential N-donors
in the ligand are coordinated. The two
organometallic complexes are monometallic and
feature trigonal zinc(II) centres coordinated to two
N-donors of the ligand, and to the C-donor of the
methyl or perfluorophenyl group (Figure 14 top).
methyl group (CSD refcode LUSQIA) and (b)
[Lc37ZnII(µ−OH)]2 featuring a bridging hydroxide (CSD
refcode LUSQOG). Redrawn from data obtained from
the CCDC as published in reference [55]. Carbon = Light
grey, Oxygen = Red, Nitrogen = Light Blue and Zinc =
Pink.
The second subset of ligands in motif C are eight
different asymmetric N2 bidentate anilido-imine
(AnIm) compounds (HLc41–50), which are
monoanionic when deprotonated (Figure 15). The
central diarylamine unit features a single imine unit
on one side which is derived from an aniline
moiety. Of the first-row transition metal complexes
prepared, 15 have been structurally characterised

18

Page 18 of 60
(see later, Section 3). These complexes are of
interest as metalloenzyme models [60] and
catalysts [61], as is detailed below.
Figure 15: Motif C: The diarylamine unit is substituted
M
at the 2-position on one phenyl ring only, by a
phenylimino unit, giving ligands HLc41 to HLc72. Ligands
HLc41 to HLc50 are often referred to in the literature as
AnIm ligands.
d
Ligand Synthesis
There are three general methods by which ligands
te
of this type are synthesised. The only difference is
the order of the diarylamine coupling and imine
formation steps. For the first method, a suitably
p
substituted arylamine is coupled with o-
bromobenzoic acid in the presence of CuO as
ce
catalyst, to yield the substituted diarylamine (58–
70%). The carboxylic acid derivative is then
converted to the acyl chloride using SOCl2, and
subsequently reacted with p-toluene-
Ac
sulfonylhydrazine to form an arylsulfonylhydrazide
(85–88%), which can be thermolysed in ethylene
glycol in the presence of base (Na2CO3) to give the
asymmetric diarylamine mono-aldehyde. The imine
compounds (HLc43 and HLc45) are produced by
subsequent reaction of the aldehyde with a suitably
substituted aniline, in refluxing benzene and using
a Dean-Stark trap, preferably in the presence of an
acid catalyst (CF3CO2H). The crude products were
then purified by column chromatography through
silica in hexane (60–76%) [62].
In the second method the imine functionality is
formed first, then the resulting precursors are
coupled with a suitably substituted aniline
derivative. For ligands HLc42 and HLc47 the imine
precursor was synthesised by stirring a solution of
o-fluorobenzaldehyde and a suitably substituted
aniline in n-hexane for 2 hrs. Purification of this
precursor was achieved by distillation under
reduced pressure (74% yield) [63]. The precursors
to HLc41, HLc45 and HLc44 are prepared in the same
t
manner. However, the former two ligands were
ip
purified by crystallisation from the n-hexane
reaction solution at −10 °C (66 and 68%) [63, 64],
and the latter ligand was purified by
cr
recrystallisation from MeOH at −10 °C (41%) [65].
For the precursor to HLc46, 2-fluorobenzaldehyde is
first nitrated (KNO3, H2SO4; 90%) before reaction
us
with the appropriate aniline in EtOH and
subsequent recrystallisation of the resulting
precipitate (67%) [66]. The coupling step of this
second method involves the nucleophilic aromatic
an
displacement of fluorine in the imine precursors by
the desired lithiated aniline derivative, giving the
respective ligands HLc41 (70%), HLc42 (41%), HLc44
(41%), HLc45 (47%), HLc46 (25%), and HLc47
(44%). This is carried out as follows; the
substituted aniline in THF is lithiated (nBuLi) at
−78 °C and added to a solution of the imine
precursor. After stirring for 1 hr the mixture is
quenched with water. Then the compound is either
extracted into hot EtOH and recrystallised; or
extracted into n-hexane, the solvent removed and
then taken up in hot MeOH or EtOH, before
crystallisation at −10 or −20 °C respectively. The
imine stretch observed in the IR spectra occurs at
1621–1623 cm−1.
A third method was used to access ligand HLc48
[67]. A solution of substituted aniline in hexane at
0 °C under N2 was added to TiCl4. After 2 hrs 2′-
fluoroacetophenone was added and subsequently
refluxed overnight. The product was extracted into
Et2O, filtered through a frit and then through Celite,
before being column chromatographed through
silica in 9:1 hexane : EtOAc (Rf 0.35), yielding the
clean imine (57%). Notably, TiCl4 was employed
since typical acid catalysed methods of imine
formation did not give the desired imine. To obtain
the ligand, a solution of substituted aniline in THF
is lithiated (nBuLi) at −78 °C, added to a solution
of the imine in THF and refluxed under N2 for 36
hrs. The mixture was quenched with water and the
product extracted into n-hexane. The solvent was
19
Page 19 of 60
removed and the product dissolved in hot EtOH
and then crystallised at −20 °C (46%).
A series of N2P and N2S donor ligands, HLc51-56
(Figure 15), were synthesised by the Jin group in
two steps.[68] First 2-fluorobenzaldehyde was
condensed with either 2-(diphenylphosphino)-
benzamine or 2-aminophenyl phenyl sulfide in
hexane to give the sulfur and phosphorous
containing precursors. These precursors were then
reacted the appropriate 2,6-disubstituted aniline
(with a NH proton first removed by nBuLi) in a
nucleophilic aromatic displacement of the fluorine
to give the series of ligands HLc51-56 (Figure 15) in
moderate to low yields of 30-43%.
Work by Mu’s group produced the N3-donor
ligands HLc65 and HLc66 (Figure 15)[69], in a
similar fashion to the ligands above by Jin’s group,
except in this instance the final amine is quinolin-8-
amine. The other two ligands, HLc57 and HLc58
(Figure 15), were synthesised in two steps. First, in
a reaction setup similar to those before, 2,6-
M
dimethylaniline or 2,6-diisopropylaniline is
coupled to 1,3-dioxolane protected 2-
bromobenzaldehyde with Pd(OAc)2 and sodium
tert-butoxide to give 2-(2,6-
d
dimethylphenylamino)benzaldehyde and 2-(2,6-
diisoproylphenylamino)benzaldehyde respectively.
te
These two aldehydes are then condensed with
quinolin-8-amine in hexane with a few drops of
formic acid to give the ligands HLc57 and HLc58 in
p
65 and 67% yield.
ce
In later work, Mu’s group continued with the same
style of ligand as above, but introduced an oxygen
donor to the ligand in the form of a phenol oxygen
attached to the nitrogen of the imine[70]. This
produced the series of N2O donor ligands HLc59-64
Ac
(Figure 15). The first step of the synthesis was as
above, in the second step the amine used in the
condensation reaction was a 2-amino-4-tert-butyl-
6-alkylphenol compound. This gave the pure
ligands in 79-88% yield.
In a patent published by Yan Wang and co-workers
the ligands HLc42-44 are claimed (Figure 15),
however no synthetic details are available.[71]
Metal Complexes
Generally, the desired metal precursors or
complexes were prepared by deprotonation of the
appropriate ligand in THF or toluene using strong
bases (NaOH, nBuLi or lithium
bis(trimethylsilyl)amide), followed by metallation
of the isolated deprotonated ligand using the metal
salt of choice. These reactions have typically been
carried out under standard Schlenk or drybox
conditions.
t
Transition-metal complexes derived from AnIm
ip
based ligands have also been developed for their
use as catalysts. Formation of aziridines
(sometimes with high ee values) by reaction of
cr
azides with alkenes, using (typically copper) metal
catalysts, has been achieved using related ligands.
Warren’s group has investigated use of such AnIm
us
ligands for such purposes [61]. Late transition-
metal olefin polymerisation catalysts have received
considerable interest since they are less oxophilic
and more tolerant of polar substituents. Catalysis
an
by diimine, β-diketiminate and salicylaldiminate
complexes with nickel and palladium has been
reported. Wu and co-workers have combined
features of the latter two ligand types to produce
sterically crowded AnIm based complexes for use,
at least in the first instance, as catalysts for the
(co)polymerisation of norbornene, styrene and
ethylene [72]. To this end, the cobalt(II), nickel(II),
copper(II) and zinc(II) complexes with derivatives
of this ligand have been investigated. Mu and co-
workers have also investigated such AnIm ligands
with chromium(III) to try and model the industrial
heterogeneous Phillips catalyst (for ethylene
polymerisation), for which the catalytic mechanism
remains unknown [73]. β-Diketiminate based
complexes have previously been used to model the
Phillips catalyst, but these are not readily
derivatised, whereas salicylaldiminate based
ligands are.
Transition-metal complexes of AnIm ligands for
use as olefin polymerisation catalysts has been
investigated, and several patented [62, 74-77]. The
resulting polymers have a variety of uses,
depending on their polydispersity, such as
thermoplastics, elastomers etc. For instance,
polynorbornene (PNBE) has a variety of different
properties, including:
“high chemical resistance, good UV resistance,
low dielectric constant, high glass transition
temperature, excellent transparency, large
refractive index and low birefringence.” (Wu et al.
[78])
20
Page 20 of 60

Polymers produced by vinyl addition type
polymerisations are favoured over ROMP due to
decreased crystallinity and increased solubility
[79]. Despite these favourable properties, vinyl
poly-norbornenes may also be very brittle at RT,
often having poor solubility in common organic
solvents (especially highly crystalline PNBE) and
poor melt processability due to high Tg values. The
solubility issues can be overcome by choice of
catalyst or use of substituted norbornene
monomers. For improved processability to obtain
more elastic optical materials, Wu’s group has also
investigated the random copolymerisation of
norbornene with styrene [80]. Ligand design is
crucial for polymerisation catalysts, where ligand
sterics and electronic properties affect catalytic
activity and polymer molecular weights. To this
end, Wu’s group have produced a structurally
characterised (see later, Section 3) nickel(II)
bromide complex with a nitro-substituted ligand for
comparison with other catalytic complexes for the
polymerisation of ethylene (Figure 16). This
M
dimeric complex features tetrahedral N2Br2
coordinated nickel(II) ions. It is far more active
(15–20 times) than the less electron-deficient
analogues [66].
d
te
p
ce
Ac
Figure 16: Crystal structure of [(Lc42)2Ni2IIBr2] (CSD
refcode FAMGIK), redrawn from data obtained from the
CCDC as published in reference [63]. Carbon = Light
grey, Nitrogen = Light Blue, Nickel = Green and
Bromine = Orange.
The (co)polymerisation of ethylene, norbornene
and styrene by transition-metal complexes
(particularly NiII) of AnIm ligands has been
investigated [62, 74-77, 81]. In most cases, co-
catalysts such as B(C6H5)3, MAO and MMAO are
required for polymerisation. Typically, MAO and
the olefin are combined in an organic solvent, such
as toluene or chlorobenzene, and the metal catalyst
is added. This occurs under oxygen and moisture
free conditions. Polymerisations have been carried
out at temperatures ranging from 0–100 °C, with
the optimal temperature around 50–70 °C. The
resulting polymer could be obtained by filtration of
t
the precipitate resulting from quenching of the
ip
reaction (often HCl acidified EtOH).
The dimeric copper(I) complexes [Lc42CuI]2 and the
cr
nitrene bridged analogue [(CuILc42)2(µ-NAr)]
(where Ar = 3,5-Me2C6H3) were prepared [61]. The
latter compound decomposes quickly in solution at
us
RT. The monomeric copper(I) complex
[Lc42CuI(MeCN)] was also prepared and could be
reacted with the desired secondary ligand (PMe3 or
CNtBu). Copper is known to catalyse aziridination
an
reactions using nitrenes such as NAr [82, 83]. For
this reason, preliminary reactivity studies were
carried out by Warren’s group using [(Lc42CuI)2(µ-
NAr)]. This complex demonstrates group transfer
of the nitrene (NAr) to strong nucleophiles, such as
CNtBu and PMe3 (giving ArN=C=NtBu and
ArN=PMe3 respectively). Reaction with weaker
nucleophiles (such as styrene) results in the
homocoupling product ArN=NAr [61].
In nature, copper–sulfur based biomolecules
generally have thiolate based active centres,
whereas relatively few are sulfide containing.
There are few examples of synthetic copper(II) µ-
sulfide complexes of nitrogen-containing ligands of
low denticity. Tolman and co-workers have led the
development of this research area, producing
dimeric sulfide-bridged copper(II) systems based
on the AnIm ligands HLc44 and HLc48 [60, 67].
The dinuclear complex [Cu2II(Lc44)2(S2)] could be
prepared in two ways (using either (TMS)2S, 29%;
or S8, 59%) [60, 84, 85]. This structurally
characterised dimeric compound (Figure 17)
features two square-planar copper(II) ions, each in
an N2S2 -donor environment, and being bridged by
a di-sulfido moiety (see later, Section 3). This
dimeric copper(II) complex is EPR silent and has
sharp signals in the 1H–NMR spectrum. This
apparent diamagnetism is attributed to a strong
antiferromagnetic coupling between the copper(II)
ions, mediated by the disulfido bridge. These
complexes have multiple intense LMCT peaks in
21
Page 21 of 60
the UV-vis spectra (in THF), attributed to ligand
based π → π* and/or (S2)2– → CuII. The d-d
transitions occur at 833 (600) for the chloride
complex and 865 nm (400 L.mol−1.cm−1) for the
disulfido bridged complex. The analogous,
structurally characterised (see later, Section 3)
compounds [Cu2II(L)2(S2)] (where L = Lc42 or Lc48)
could also be prepared using the second method
[60, 84].
M
d
te
p
ce
Figure 17: Crystal structures of (top) monomeric
[Lc44CuI(MeCN)] (CSD refcode EZOFEE) and (bottom)
dimeric [(Lc44)2Cu2II(S2)] • MeCN • C5H12 (CSD refcode
EZOFOO) complexes, redrawn from data obtained from
the CCDC as published in reference [60]. Carbon = Light
Ac
grey, Nitrogen = Light Blue, Copper = Orange and Sulfur
= Yellow.
Exchange of the bound disulfide or acetonitrile
with PPh3 or xylyl isocyanide in C6D6 was also
investigated (using 1H– and 31P(1H)–NMR
spectroscopy), in order to draw some conclusions
about the reactivity of such systems [84]. Four
equivalents of PPh3 were reacted with one
dinuclear complex to give two equivalents each of
the [CuI(Lc42)(PPh3)] and SPPh3 products. In
contrast, only two equivalents of the isocyanide
were required to produce [CuI(Lc42)(CNAr)]
quantitatively [84]. The fate of the S22– fragment in
the latter case was not established. This compound
did not react with O2 or CO. These complexes are
deeply coloured due to multiple intense transitions
in the absorption spectra, attributed to disulfide π*
→ CuII (between 350–500 nm). The spectra also
contain weaker peaks attributed to d-d transitions,
between 550–880 nm. Both 32S8 and 34S8 were
used, with resonance Raman showing an isotope
t
dependent S–S stretch (300–550 cm−1). Tolman and
ip
co-workers concluded that increased Cu–S bonding
interactions result in longer S–S bonds, that is
greater S–S bond activation (due to backbonding
cr
from the filled Cu dxy orbitals into the empty (S2)2-
σ* orbital). Interestingly, addition of HLc42 to a
DCM solution of [Cu2II(TMEDA)(S2)] results in
us
clean conversion to the more thermodynamically
stable anilido-imine based dimer, [Cu2II(Lc42)2(S2)]
[85].
an
The µ–η2:η2-disulfido bridged complex
II c34
[Cu2 (L )2(S2)] and some oxygen-bridged analog-
ues were also investigated theoretically by utilising
DFT calculations [60, 86]. This study established
that the (µ-η2:η2-peroxo)- and bis(µ-oxo)-bridged
forms are attainable, as seen experimentally. In
contrast, only the (µ-η2:η2-disulfido)dicopper(II)
complex is accessible. The addition of various
terminal ligands did not stabilise the sulfido-
bridged dimer, but it was proposed that a two-
electron reduction would cleave the S–S bond and
give a (Cu2(S)2) core [86].
The Tolman group is also interested in copper–
oxygen complexes incorporating ligands such as
HLc48 due to their potential as biomimetic models
for dopamine β-monooxygenase and peptidyl-
glycine α-hydroxylating monooxygenase [87].
Various monocopper–oxygen based species have
also been postulated as intermediates in various
enzyme mechanisms. Both end-on (η1) and side-on
(η2) superoxo-bound copper(II) structures have
been suggested. Tolman’s group had investigated
the oxygen-bound copper complexes of highly
related diketiminates, and identified problems
associated with electrophilic attack at the central
methine position. This led to their use of the more
robust ligands HLc44 and HLc48 (Figure 15) for
these studies [67, 84, 88]. Computational
characterisation of various 1:1 Cu–O2 adducts of
HLc48 was undertaken by Tolman and co-workers
in order to understand their inertness with respect
to C–H bond activation reactions [88]. It seems that
22
Page 22 of 60
the overall lack of reactivity towards substrates is
due to the weakness of the O–H bond formed upon
hydrogen atom abstraction. However, a CuIII–oxo
species was predicted to be far more reactive
towards substrates. This study concluded that
future ligands should be designed to be more
electron deficient or neutral rather than anionic, so
as to favour end-on (as opposed to side-on)
dioxygen coordination in such adducts.
The structurally characterised trigonal-planar
complex [CuI(Lc48)(MeCN)] was prepared by
Tolman and co-workers (see later, Section 3) [67].
It is highly reactive with dioxygen in solution and
in the solid state, developing a dark brown colour.
The resulting material was found to contain several
unidentified decomposition products. Both 16O2 and
18
O2 were used, with resonance Raman showing an
isotope dependent O–O stretch (900–980 cm−1),
consistent with bound peroxide. The formation of a
yellow-green intermediate at low temperature (−80
°C) is dependent on oxygen and complex
concentration and also solvent. This species was
M
shown to be a 1:1 Cu:O2 adduct. The structure
determination of [Cu(Lc48)(η2−O2)] reveals a
symmetrical side-on binding mode (Figure 18, also
see later, Section 3) [67]. The combination of
d
structural, electronic and vibrational data is
consistent with a predominantly CuIII–peroxo
te
character, rather than CuII–superoxo, for these
compounds. The side-on binding was rationalised
with a computational study, wherein the singlet
side-on form is 3.5 kcal.mol−1 more stable than the
p
end-on singlet and 14.1 and 19.4 kcal.mol−1 than
ce
the side-on and end-on triplet forms. This study
showed that the anionic ligand stabilises the
oxidised copper and promotes activation of
dioxygen [67].
Ac
Figure 18: Crystal structure of [Lc48CuIII(µ−O2)] (CSD
refcode NAXLEE), redrawn from data obtained from the
CCDC as published in reference [67]. Carbon = Light
grey, Oxygen = Red, Nitrogen = Light Blue and Copper
= Orange.
The EPR-active nickel(I) complexes
[Lc44NiI(PPh3)] and [Lc47NiI(PPh3)] were prepared
and structurally characterised by Jin and co-
workers (see later, Section 3) [72]. Notably, the
nickel(II) ions are reduced during the reaction,
t
producing trigonal-planar nickel(I) complexes, and
ip
biphenyl as a by-product. The imine stretches fall
in the range 1606–1608 cm−1. Upon activation by
MAO, these complexes have high catalytic activity
cr
(107 g.(mol Ni)−1.hr−1) for the polymerisation of
norbornene [72, 76, 77]. These unusual, low-valent
complexes are highly active, simply prepared and
us
have good stability. Polymerisation of norbornene
by these catalysts results in non-crystalline PNBE
with high molecular weights (106 g.mol−1), high
glass transition temperatures and good solubility.
an
The highest activity and molecular weights were
observed at Al:Ni ratios of 5000. Interestingly, no
activity was observed at a ratio of 1000. The
molecular weight also varied with temperature,
being highest at 60 °C. The less hindered complex,
derived from HLc47, exhibited even greater activity.
A range of dark green nickel(II) complexes were
prepared by Wu and co-workers, having formulae
[LNiIIBr]x where L = Lc42, Lc44, Lc45, Lc46 and Lc47
(Figure 15) and where x = 1 (monomeric) or 2
(dimeric) [63, 66]. Three of these were structurally
characterised, with all three being dinuclear
complexes with the nickel(II) ions in a tetrahedral
N2Br2-donor environment (see later, section 3). By
analysis of the 1H−NMR spectra in deuterated
benzene or toluene, the monomer:dimer ratio could
be established in these solvents. These values
varied from 2.5–13.3:1 monomer:dimer, with the
monomer the main species present in all cases. At
elevated temperatures only the monomeric complex
was observed. The 1H–NMR resonances of these
paramagnetic complexes varied from 60 to −100
ppm. Equilibrium constants were obtained at a
variety of temperatures and the enthalpy and
entropy terms for two of the complexes were
established. Pushing the monomer:dimer
equilibrium towards the monomer is enthalpically
disfavoured and entropically favoured. It was
suggested that such ligands, compared to
diketiminates, are less likely to dimerise on the
basis of ∆H values for the monomer:dimer
equilibrium for each ligand system. As might be
anticipated, bulky substitution was found to further
23
Page 23 of 60
favour the monomeric form. In solution, this
equilibrium can also be monitored by UV-vis
spectra, wherein the three-coordinate monomer has
an intense band at 708 nm, whereas the four-
coordinate dimer has a weak band at 517 nm.
The nickel(II) complexes, [LNiIIX] (where L = Lc43,
Lc45 and Lc46, Figure 15; and X = Br, methyl
methacrylate), have been shown to polymerise
ethylene (at 1 atm) in conjunction with a co-
catalyst such as B(C6H5)3, MAO or MMAO [62,
66]. These complexes showed good activities (up to
4.4 × 105 g.(mol Ni)−1.hr−1) at Al:Ni ratios of ca.
400.
The nickel(II) complexes, [LNiIIBr] (where L =
Lc41, Lc42, Lc44, Lc45, Lc47, Figure 15), have been
investigated for the polymerisation of various
olefins. Attempted polymerisations of ethylene
using these metal catalysts in the presence of MAO
result in only low molecular weight oligomers
being produced[90]. These compounds do,
however, have good catalytic activity for the
M
polymerisation of norbornene in the presence of
MAO (6.8 × 106 g.(mol Ni)−1.hr−1) [63, 74, 79, 80,
89] but generally lower than comparable complexes
with [N,N] six-membered chelating ligands (β-
d
diimines, β-diketiminates or fluorinated β-
diketiminates). This was attributed to the AnIm
te
ligands having less positive character on the nickel
centre in the active species and thus lower activity.
It was found that the more sterically hindered
nickel(II) complexes (Lc44 vs. Lc42) gave higher
p
catalytic activities and higher molecular weights
ce
[78]. The resulting poly-norbornene exhibits low
stereoregularity and was produced by a vinyl-
addition type mechanism (as opposed to
cationic/radical or ROMP). The presence of two
(LNiIIMe
Ac
catalytic species and
II
LNi (µ−Me)2AlMe2) below 50 °C was identified in
one study by Wu’s group [79]. This resulted in a
bimodal molecular weight distribution in the
resulting polymeric material (clearly seen in GPC
curves), and thus a large molecular weight
dispersity. Above 50 °C, only the monometallic
species was present, resulting in polymers with
higher average molecular weights and narrower
dispersities. No induction period was observed for
these polymerisations, consistent with rapid
formation of the active catalyst species. The
resulting polymers were stable up to 450 °C and
soluble in chlorobenzene, o-dichlorobenzene and
cyclohexane at RT. The copolymerisation of
norbornene with styrene was also investigated [80].
It was found that the weight-average molecular
weights of the copolymers are low and dependent
on styrene content. The styrene content of the
resulting copolymer is always lower than that of the
initial content in the monomer feed, due to the
much higher reactivity of norbornene compared to
t
styrene. Notably, the styrene content increases with
ip
an increase in the polymerisation temperature.
Wu’s group have also investigated the homopoly-
merisation of styrene by these nickel(II) complexes
cr
[89]. It was found that the complexes with ligands
having bulkier R2 substituents (Lc44 and Lc45)
slightly reduced the catalytic activity. The highest
us
activity of these complexes was observed for
[Lc44NiIIBr], at 70 °C with an Al:Ni ratio of 775, of
up to 8.69 × 105 (g PS).(mol Ni)−1.hr−1. The
polymer molecular weight increased with a
an
decrease in the temperature and an increase in the
steric bulk of the complex. The average length of
isotactic sequences was about twice that of
syndiotactic sequences. All of the obtained
polymers were completely soluble in THF, methyl
ethyl ketone and acetone.
The trigonal-planar zinc complexes [Lc44ZnIIEt] and
[Lc44ZnIIN(SiMe3)2] were prepared, crystallised and
the structures (see later, Section 3) compared to
those of related β-diketiminate based derivatives
[55]. The highly related complexes, [LZnX] (where
L = Lc42, Lc43 and Lc44, Figure 15; and X = Me, Et,
OAc, OBz), have been patented for their ability to
catalyse the (co)polymerisation of various lactones
and/or lactides (such as glycolide, lactide, β-
butyrolactone, β-valerolactone or ε-capro-lactone)
[75]. It is claimed that such metal catalysts have
good stability, high catalytic activity and can
produce block, random or homopolymers of such
monomers.
The cobalt(II) complex [Lc44CoII(µ−Cl)2Li(THF)2]
was prepared and structurally characterised (see
later, Section 3). The cobalt(II) ion is in a
tetrahedral N2Cl2-donor environment, with both
chloride ions bridging to a lithium ion. The
polymerisation of norbornene was achieved using
this catalyst in conjunction with MAO in CB under
a nitrogen atmosphere [90]. After a given time the
reaction was quenched and the polymer
precipitated by addition of acidic MeOH. The
highest activity (25.5 × 105 g.(mol Co)−1.hr−1) was
24
Page 24 of 60
observed using the ratio [NB]:[Al]:[Co] of
100,000:3,000:1, and gave high molecular weight
products (1.43 × 106 g.mol−1) with low
stereoregularity. Attempts to polymerise ethylene
were also carried out, but resulted in only trace
amounts of polymeric material.
The complexes, [LCrIIICl2(THF)2] (where L = Lc42,
Lc44, Lc45) were prepared and tested for their ability
to catalyse the polymerisation of ethylene [73].
Two other chromium(III) complexes, derived from
HL49 and HL50, were prepared and structurally
characterised (Figure 19). These two ligands
(Figure 15) do not fit the search fragment (Figure
1), but are clearly very closely related. In these
structures the chromium(III) ion is in an octahedral
N2O2Cl2-donor environment (see later, section 3).
M
d
te
Figure 19: Crystal structure of [Lc49CrIIICl2(THF)2]
(CSD refcode YUTZUJ), redrawn from data obtained
from the CCDC as published in reference [73]. Carbon =
p
Light grey, Oxygen = Red, Nitrogen = Light Blue,
Chromium = Pink and Chloride = Chloride.
ce
In the polymerisation tests, the catalyst of interest,
in conjunction with MAO, was reacted in toluene
with ethylene (1 bar) in a steel autoclave [73]. The
Ac
ethylene pressure was maintained for 30 min, after
which the polymerisation was quenched using
(HCl) acidified MeOH and the resulting
precipitated polymer isolated. In conjunction with
the co-catalyst MAO, optimal activity for the
polymerisation of ethylene occurred at 20 °C.
Higher temperatures resulted in lower activities,
attributed to the lower ethylene solubility at higher
temperatures and catalyst decomposition. The
highest activity was observed at an Al/Cr ratio of
500. Under these conditions, the catalysts had the
following activity, ligand (×106 g.(mol Cr)−1.hr−1):
Lc42 (1.37), Lc44 (0.29), Lc45 (0.34). Ligands with
greater steric bulk had higher activity, attributed to
greater cation···anion separation and shielding of
the active site; but increasing the steric bulk too
much resulted in lower activity, due to slowing of
ethylene coordination and hindering of chain
propagation. Analysis of the 13C−NMR spectra
revealed long-chain branches, with branching
occurring at 5 per 1000 C atoms.
t
Jin’s group used the series of ligands HLc51-56
ip
(Figure 15) to form nickel(II) [and palladium(II)]
complexes[68], of general formula [LxMIICl]. The
complexes were tested as catalysts for norbornene
cr
polymerisation to yield vinyl addition type
polynorbornene (PNB). The results showed that all
of the nickel(II) complexes displayed some
us
activity, up to 5.82 × 107 g.mol-1.h-1 of PNB. In
contrast, the analogous palladium(II) complexes
showed poor to no catalytic activity.
an
As with Jin’s work, the four ligands (HLc57,58,65,66,
Figure 15) synthesised by Mu’s group[69] were
reacted with nBuLi and NiCl2(DME) to give
complexes of general formula [LxNiIICl]. The
complexes of ligands HLc58 and HLc66 were
structurally analysed by X-ray crystallography (see
later, Section 3). When combined with MAO all of
these complexes showed activity in the same
norbornene polymerisation reaction studied in Jin’s
work.
In a later paper, Mu’s group[91] synthesised the
ligands HLc59-64 (Figure 15) in similar fashion to
their earlier work. These ligands however were
complexed to titanium for use as catalysts of
ethylene polymerisation. Initially the complexation
reactions were performed at room or lower
temperatures, however the complexes formed were
zwitterionic, [(H2Lc59-64)+Ti-(Cl4)]. Heating of these
complexes to 40 °C gave the neutral [HLc59-64TiCl3]
and then further heating to 140 °C yielded the
desired complexes, [Lc59-64TiCl2]. These complexes
were tested for their ability to catalyse ethylene
polymerisation. The results showed that the ligands
with adamantyl groups gave higher catalytic
activity compared to the tert-butyl substituted
ligands. Overall catalytic activity of these ligands
increased as the size of the aryl group on the amido
nitrogen increased.
In a patent published by Wang and co-workers[71]
the ligands HLc42-44 (Figure 15) were coordinated to
zinc(II) to give [Lc42-44ZnEt]. The patent abstract
25
Page 25 of 60
describes these complexes as efficient catalysts for
the ROP of ɛ-lactide. As this is a patent abstract no
further information or data is given to support this
claim.
In a patent published by Zhang, Ai and Xie[92] a
wide variety of complexes is reported for use in the
preparation of linear low-density polyethylene
using a bifunctional catalyst system. One of the
complexes listed in the patent is [(Lc67)2TiIVCl2],
but its exact role is not defined.
Ligand Synthesis
Black’s group prepared 2,2′-iminobisbenzaldehyde
in a 2-step synthesis from the corresponding diester
[36, 93] by LiAlH4 reduction followed by MnO2
oxidation, in 90 and 60% yields respectively [94].
In contrast, Matsui and co-workers proceed directly
to the dialdehyde by reduction of the diacid in THF
at −20 °C, using bis(1-methylpiperazine-4-
yl)aluminium hydride [81]. The resulting oil was
purified by column chromatography through silica
in modest yield (34%). The latter group also
M
synthesised the Schiff base ligand HLc68 by
condensation of the dialdehyde with 2,6-dimethyl-
aniline (Figure 20) under argon and in the presence
of catalytic amounts of acetic acid in MeOH. The
d
resulting crude ligand was purified by column
chromatography through silica in modest yields
te
(19%). The mobile phase was not reported for
either purification.
p
ce
Ac
Figure 20: Motif C: The diarylamine unit in which both
phenyl rings are substituted at the 2-position by a
phenylimino unit.
Metal Complex
The five-coordinate iron(III) complex [Lc68FeIIICl2]
was prepared in good yield (85%) by reaction of
FeCl2 with lithiated, deprotonated ligand (LiLc68) in
THF, followed by filtration (to remove impurities),
concentration and finally precipitation by adding
pentane. When present with the co-catalyst MAO,
this compound polymerises ethylene in toluene at
room temperature and pressure. The polymerisation
activity was 4×103 g.(mol Fe)−1.hr−1.
Ligand Synthesis
Eisenberg and co-workers investigated a series of
copper(I) complexes using ligands, HLc69-74 (Figure
21), for their potential photoluminescence[95]. All
of the ligands used featured a triazole group off one
of the phenyl rings and a variety of substituents on
the other. These ligands were synthesised by aryl
t
amination of bromophenyl-triazole with the desired
ip
aniline derivative. In a drybox, bromophenyl-
triazole, palladium acetate, 1,1’-bis-
(diphenylphosphino)-ferrocene (dppf), sodium tert-
cr
butoxide and toluene were loaded into a Schlenk
tube and stirred before the desired aniline was
added as a solid or in a solution with toluene. The
us
tube was then sealed with a Teflon stopper and
heated at 100 °C for 48 h. After quenching with
water, the crude product was extracted into CH2Cl2,
then purified by column chromatography (5:1
an
hexane:ethyl acetate), to yield the respective
ligands in good yields (85-43%).
Figure 21: Motif C: The diarylamine unit in which one
phenyl ring is substituted at the 2-position by a triazole
unit. When not specified, R1 = H, R3 = H.
Metal Complexes
The copper complexes of these ligands were
prepared by addition of potassium tert-butoxide to
a THF solution of the desired ligand followed by
dropwise addition of this solution to a slurry of
[CuCl(dppb)]2 with stirring and gentle heating (<40
°C) then filtered through Celite and reduced in
volume to 1-2 mL. Addition of hexane caused
precipitation of the products, [CuI(Lc69-c74)(dppb)].
These complexes were designed with the intention
of them acting as photoluminescent compounds for
use in OLEDs. They showed modest solution
emission and strong solid state emission. Variation
of the substituent on the triazole ring created a shift
in the assignment of the excited state from MLCT
+ ILCT to MLCT + LLCT.
2.4 Motif D — Macrocyclic Diarylamine Based
Systems
26
Page 26 of 60

As for the acyclic motif C ligand HLc68 (Figure 20),
in motif D both aryl rings are singly substituted at
the 2-position by imines, but in this case they form
[1+1] and [2+2] macrocycles (Figure 22). Roughly
one tenth of the 385 complexes feature this motif.
Prior to 2011, all such compounds were synthesised
by metal-templated Schiff base condensation
reactions of 2,2′-iminobisbenz-aldehyde with the
appropriate diamine [94, 96, 97]. Until 2011, only
one of the resulting complexes was structurally
characterised [97], but another 8 have been
reported since then and prior to April 2014[98-
100].
Generally, the dialdehyde (2,2′-iminobisbenz-
aldehyde), metal salt and diamine were refluxed in
MeOH or EtOH under a nitrogen atmosphere,
thereby forming the macrocycle in a metal-
templated reaction. Three ways of preparing the
target macrocyclic complexes were reported: either
the hydrated metal perchlorate salt was used and
the product precipitated directly; or the metal
M
chloride or tetrafluoroborate salt was used instead,
followed by precipitation of the ClO4–, BPh4– or
PF6– salt by addition of solutions of excess NaClO4
d
p te
ce
Ac
(in EtOH), NaBPh4 (in EtOH) or NH4PF6 (in
methanolic pyridine) respectively; or the metal
acetate salt was used, producing neutral
macrocyclic complexes. In many of the reactions
base was added (TEA or pyridine) to remove acidic
protons and/or act as apical ligand. Generally the
complexes formed were recrystallised from DMF
or DMF mixed with MeOH or EtOH.
t
ip
Since 2011, work published by the Brooker group
has shown that [1+1] macrocyclic ligands HLd1 and
HLd2 (Figure 22) are able to be synthesised in a
cr
metal-free fashion using a direct 1:1 reaction of the
dialdehyde with the appropriate diamine[98, 99,
101]. The 14-membered macrocycle HLd1 was
us
synthesised in quantitative yields by addition of the
dialdehyde and diamine in MeCN and refluxing for
3 hrs. The pure product was then isolated, as a
yellow solid, by in vacuo removal of the solvent.
an
In contrast, the synthesis of the larger, 16-
membered, [1+1] macrocycle HLd2 was not quite so
straightforward, but the slightly impure oil obtained
was used successfully in complexation reactions.
The macrocycle HLd1 has also been reduced, using
NaBH4, to the amine analogue[99].
27
Page 27 of 60
Figure 22: Motif D: [1+1] and [2+2] imine macrocycles derived from 2,2′-iminobisbenzaldehyde and thirteen different
diamines. The diamines used are shown alongside the respective macrocyclic ligand numbering.
d11-13
The [2+2] Schiff base macrocyclic ligands H2L
(Figure 22), which varied in the length of the alkyl
chain in the diamine (ethylene, propylene and
butylene, respectively), and hence in the ring size
(22-, 24- or 26-membered) were also synthesised
metal free. The macrocycles were obtained in high
yields by refluxing a MeOH solution of the
aldehyde and chosen diamine for 2 hrs, during
which time the pure product precipitated. The
product was simply filtered off, washed with cold
MeOH and dried. There was no need to use dilute
solutions for these direct cyclisations.
Complexes of tetradentate monoanionic
macrocycles
an
The cobalt(II), nickel(II) and copper(II) complexes
of H2Ldl, H2Ld2, H2Ld3 and HLd4, monometallic
MII(HLd1-3)(ClO4) and MII(Ld4)(ClO4), were
initially prepared with perchlorate counterions [94,
M
96]. In all of these complexes, the tetradentate
macrocycle is singly deprotonated, but a base
(TEA) was only required in the reactions of
aromatic diamine derived macrocycles H2Ld3 and
HLd4. The cobalt(II) and copper(II) complexes of
d
H2Ld4 were proposed to be square-pyramidal (ClO4-
on the axial site), whereas the metal ions in all
te
other complexes were suggested to be in square-
planar environments with ionic ClO4- anions.
Notably, attempts to produce the zinc complexes of
p
H2Ld1 and H2Ld2 were unsuccessful. This was
attributed by the authors to the formation of zinc
ce
hydroxide in the presence of the basic triamines.
None of the above complexes were structurally
characterised.
Ac
In subsequent work with HLd1, by Brooker and co-
workers, seven mononuclear complexes were
prepared using Zn(II), Cu(II), Ni(II), Co(II),
Fe(III), Co(III). In all of these complexes the
macrocycle was deprotonated at the diaryl amine
nitrogen atom: in some cases this deprotonation
was aided by a base (TEA or pyridine). For the
cobalt complexes, the Co(II) oxidation state was
obtained when a non-coordinating BF4 anion was
used, however when a coordinating thiocyanate
anion (SCN) was used the resulting complex air
oxidises to Co(III). For the iron complexes, both
BF4 and SCN anions gave Fe(III) complexes. The
crystal structures of several of these complexes
were obtained and show that the ligand HLd1
provides a square planar N4 donor system which
leads to range of square planar, square pyramidal
and octahedral geometries (see later, section 3)
[101]. The nickel(II) complexes of HLd1 (square
planar) and the amine analogue of HLd1 provided a
t
ip
good example of ligand field tuning by variation of
imine vs amine donors. When coordinated to two
imines the nickel(II) ion was low spin, and it was
cr
high spin when coordinated to two amines.
However in the mixed imine plus amine complex
the spin state is determined by the presence of
us
coordinating co-ligands (high spin) or non-
coordinating co-ligands/solvent[99].
Complexes of tetradentate dianionic
macrocycles
In this case, the coordinated macrocycles are
doubly deprotonated, so with a dication metal ion
no counter anions were required [94, 96]. The
cobalt(II), nickel(II) and copper(II) complexes of
H2Ld5, H2Ld6 and H2Ld7 were prepared, all in the
presence of base (TEA). Only the nickel(II)
complex of H2Ld8, [NiIILd8], could be prepared in
pure form. The complexes were intensely coloured.
For instance, complexes derived from H2Ld7 had
bands in the region 290–570 nm with extinction
coefficients of 9000–35000 L.mol−1.cm−1. All
complexes were assigned to be in a square-planar
coordination environment, except those of H2Ld5,
for which molecular models indicated significant
buckling and deviations from planarity. This is
supported by the much lower molar absorptivity
values for these complexes.
Pentadentate macrocyclic complexes
Formation of H3Ld9 with copper(II) and zinc(II)
perchlorate salts as templates, without the addition
of a base, resulted in complexes the authors
tentatively assigned as [H2Ld9CuII]ClO4 and
[HLd9Zn], with the macrocycles assigned as
conferring a pentagonal-planar coordination
geometry [94, 96]. However, a square-pyramidal
geometry could not be ruled out. The former
complex was made under a nitrogen atmosphere.
Lewis and co-workers prepared two cobalt(II)
complexes of HLd10 with PF6– and BPh4–
counterions in the presence of pyridine [97]. X-ray
quality crystals of the latter complex were obtained
by slow evaporation from MeNO2 (Figure 23, top,
28
Page 28 of 60
see also Section 3), confirming the presence of a
pentagonal-bipyramidal cobalt(II) centre.
Electrochemistry of this complex in MeCN shows a
quasi-reversible oxidation at +0.11 V vs.
Ag/AgNO3 (∆E = 78 mV).
Hexadentate macrocyclic complexes
Cameron and Brooker reported the metal free
synthesis of the three [2+2] Schiff base
macrocycles H2Ld11-13 (Figure 22) from the
dialdehyde and an appropriate 1,n-diaminoalkane
(n = 2, 3 or 4) [100].
M
d
te
p
ce
Figure 23: Crystal structure of (top) [Ld10CoII(Py)2]BPh4
(CSD refcode BOJTOJ), redrawn from data obtained
from the CCDC as published in reference [97] and
Ac
(bottom) [Ld11CuII2(OAc)2] image as published in
reference [100]. Carbon = Light grey, Oxygen = Red,
Nitrogen = Light Blue, Cobalt = Navy Blue and Copper
= Green.
These structurally characterised macrocycles were
then complexed with copper(II) giving six
complexes: two of each ligand, with either acetate
(3 hr reflux in dry MeOH; orange brown products)
or pyridine (30 min reflux in IPA/pyridine; anion =
BF4; golden-brown to brown products) also
coordinated. As anticipated, given the bis-tridentate
nature of these macrocycles, in each case two
copper(II) ions are accommodated within the
hexadentate ditopic macrocycle. Ligand based
oxidations were a feature of all macrocycles and
complexes, and there was evidence of
electropolymerisation occurring for two of the
acetate complexes in DCM. The CuII/CuI redox
potential was lower (easier to oxidise) for the
acetate than for the tetrafluoroborate dicopper(II)
complexes. Four of these dicopper(II) complexes
have been structurally characterised (Figure 23,
t
bottom), so the structures are discussed further in
ip
Section 3.
2.5 Motif E — Acyclic and Macrocyclic
cr
Bis(diarylamine) Based Systems
This motif is symmetrical and contains two
us
diarylamine units connected to one another. They
are connected either directly (Figure 24), or by
some bridging unit, either a pyridine ring (see later
Figure), a diiminoalkyl chain (see later Figure), or
an
an ortho-terphenyl and/or ortho-phenyl moiety (5
of these ligands are macrocyclic) (see later Figure).
Roughly one seventh of the 385 complexes feature
ligands from this motif; fourteen such complexes
have been structurally characterised.
Ligand H2Le1 (Figure 24) has two diarylamine units
singly joined to each other at the 2-position of one
of the aryl groups, and tert-butyl substituted
oxazole groups on the 2′-positions of both
diarylamine units [2]. This ligand has a potentially
tetradentate N4-donor binding pocket. The
copper(I) complexes of such oxazaline based
ligands are frequently used for asymmetric
synthesis, such as the highly enantioselective
synthesis of sirenin reported by Corey and co-
workers [102].
29
Page 29 of 60
Figure 24: Motif E: Two diarylamine units connected
directly and with flanking oxazole rings.
Ligand Synthesis
This oxazole based ligand (Figure 24) was
synthesised by a palladium-catalysed Buchwald–
Hartwig type coupling of 2,2′-diamino-biphenyl
with the 2-(2′-bromophenyl)oxazoline derivative
from the CCDC as published in reference [2]. Carbon =
Light grey, Oxygen = Red, Nitrogen = Light Blue and
Copper = Orange
Ligand H2Le2 (Figure 26) has two diarylamine units
joined to each other by a bridging pyridine at the 2-
position of one of the two aryl rings, and the
second aryl ring is a mesityl group. This ligand

t
[2]. Notably, the first arylation occurs much more forms a dianionic tridentate binding pocket.

ip
quickly than the second, so the mono-arylated
compound can be isolated, allowing
asymmetrically substituted ligands to be prepared

cr
by a second palladium-catalysed arylation.

Metal Complexes

us
The only complex of this ligand type is a
structurally characterised monometallic copper(I)
complex, [H2Le1CuI]PF6, where neither amine is
deprotonated and so there is a PF6 counterion

an
(Figure 25) [2]. NMR studies show the formation
of this complex from a mixture of diastereoisomers
to be rapid and highly diastereoselective, resulting
in a diastereopure product that shows no sign of
M
diastereoconversion. The structure determination
shows the oxazole nitrogen atoms bind to the
copper(I) centre in a near linear fashion (169.11°), Figure 26: Motif E: Two diarylamine units connected by
whereas the two aryl amines retain their protons a pyridine bridge (blue/red lines are the two ways this
ligand can fulfil the search criteria).
d
and are only weakly bound (2.640 and 2.838 Å).
The absolute configuration of the coordinated
Ligand Synthesis
ligand was established from the crystal structure.
te

Ligand H2Le2 was prepared in two steps, both

DFT studies showed an energy barrier to
coupling reactions [103]. Firstly, 2-bromoaniline is
diastereoconversion of 26 kcal.mol−1, supporting
borylated using pinacolborane, Pd(OAc)2 and TEA
the formation of a single non-interconverting
p

(in dioxane) at 80 °C under Ar; and this

diastereoisomer. The formation of single
intermediate is reacted in situ with 2,6-
diastereopure complexes is a key step for
ce

dibromopyridine, Ba(OH)2•8H2O and water at 101

producing effective asymmetric catalysts.
°C. The crude diamine intermediate could be
purified by column chromatography through silica
in DCM and was isolated in 33% yield. This
Ac

intermediate was Buchwald–Hartwig coupled with

an excess of mesityl bromide using Pd2(dba)3, rac-
BINAP and NaOtBu (in toluene) at 120 °C under
Ar. The final product, H2Le2, was purified by
removal of excess aryl bromide by vacuum
distillation, followed by filtration through a silica
plug (in DCM) and washing (with MeOH) to give
an off-white solid in 46% yield.

Metal Complexes
Noble metals have typically been employed in
catalysts due to their redox behaviour (two-electron
redox couples) and tolerance to oxygen, water
Figure 25: Crystal structure of [H2Le1CuI]PF6•CH2Cl2
(CSD refcode JENJAO), redrawn from data obtained
and/or various functional groups. However, such

30

Page 30 of 60
metals come with a large price tag and
environmental impact and this has provided the
incentive for groups such as Bercaw and co-
workers to investigate metals such as iron, which
are cheap and relatively benign [103].
The iron(II) complex [Le2FeIITHF] was prepared as
the lithium chloride adduct, initially deprotonating
the ligand with Me3SiCH2Li in toluene. The
complex free of LiCl was obtained by dissolving
the adduct in toluene, diluting with PE and
crystallisation at −30 °C. Structural characterisation
(see later, section 3) revealed a neutral complex
featuring a distorted tetrahedral iron(II) centre with
an N3O-donor set. Cyclic voltammetry studies were
carried out on [Le2FeII(THF)] in THF and showed a
quasi-reversible reduction at −0.96 V (presumably
ligand based) and an irreversible oxidation at −0.37
V, vs. Fc/Fc+. Hence it was chemically oxidised,
using molecular iodine to produce [Le2FeIIII]
(Figure 27); or by dioxygen to produce the dimeric
(bridging oxo) material [{Le2FeIII}2O]. Both
iron(III) complexes were structurally characterised,
M
with the iron(III) ions also having closer to a
tetrahedral geometry, with N3I- and N3O-donor sets
respectively (see later, section 3). The 1H−NMR
spectra of these paramagnetic complexes (5 and 6
d
u.p.e) were taken, with resonances in the range
−209 to 138 ppm. The magnetic moments were
te
also measured in solution via the Evans method in
d6-benzene and agree with the anticipated quintet
(4.8 B.M. for FeII THF complex) and sextet ground
states (5.8 B.M. for FeIII iodide complex). The UV-
p
vis spectrum of the ligand has a number of
ce
absorbances below 400 nm. The spectra of the
complexes have additional peaks or shoulders
above this, for instance in [Le2FeIIII] at 741 nm
(7300 L.mol−1.cm−1) or in [{Le2FeIII}2O] at 649 nm
(6800 L.mol−1.cm−1). No attempt was made to
Ac
assign these transitions.
t
ip
cr
us
Figure 27: Crystal structure of [Le2FeIIII] (CSD refcode
YUBDEF), redrawn from data obtained from the CCDC
as published in reference [103]. Carbon = Light grey,
an
Nitrogen = Light Blue, Iron = Orange and Iodine =
Purple.
In later work the Bercaw group[104] used the same
ligand (H2Le2), but initially deprotonating it using
KBn in toluene, then introducing the titanium(IV),
to form a series of complexes, [Le2TiCl2],
[Le2TiCl2(THF)], and [Le2Ti(NMe2)2]. The
preparation of [L TiCl2] or [Le2TiCl2(THF)] was
e2
dependant on reaction solvent (toluene or THF).
The formation of the THF adduct caused a shift
from five-coordinate C1-symmetric geometry in the
former to a six coordinate C2-symmetric complex
for the latter. This shift was monitored by variable
temperature 1H-NMR spectroscopy. All of these
complexes were tested as propylene pre-catalysts,
with results showing low to moderate activity
(102−104 g.mol-1.h-1).
The symmetrical ‘half macrocycle’ ligands in
which the two diphenylamine moieties are linked
by a diiminoalkane shown in Figure 28, are
effectively ditopic versions of the monotopic AnIm
ligands described earlier, in Motif C HLc41 to
HLc50, Figure 15). On deprotonation, all four of
these ditopic ligands feature two monoanionic
bidentate binding pockets, so can accommodate
two metal ions. Such ligands have been produced
by Gibson and co-workers in efforts to produce
dimetallic zinc(II) compounds that exhibit
cooperative reactivity between the zinc(II)
centres[105], as seen in nature (such as
phosphomonoesterase enzyme alkaline phosphatase
[106]) and in conventional catalysis (such as
31
Page 31 of 60
similar β-diiminate based dizinc compounds [107];
shown to catalyse the copolymerisation of
cyclohexene oxide with CO2). Similarly, the
aluminium/zinc heterometallic catalyst has been
prepared for the same reason [108]. The aliphatic
chain length was varied to allow for differing
separation of the two metal centres. Methyl and
isopropyl substituents were used to compare the
polymerisation activity with the steric bulk. Such
ligands have been synthesised with the hope they
show ROP activity [40].
M
d
Figure 28: Motif E: The diarylamine unit is substituted
at the 2-position by an alkyldiimine, producing a bis-
te
bidentate ligand.
Ligand Synthesis
p
Initially, Schiff base condensation of 2-
fluorobenzaldehyde with the appropriate diamine
ce
gave the precursor diimines. Gibson and co-
workers synthesised the propylene- and
hexamethylene-linked compounds, in 89 and 91%
yield respectively, by reaction in n-hexane for 12
Ac
hrs [105]. Mu and co-workers prepared the
ethylene-linked compound by reaction in MeOH
for 12 hrs, giving a much poorer yield (59%) [40].
Coupling of these diimine compounds with two
equivalents of lithiated 2,6-di-isopropylaniline or
2,6-dimethylaniline could then be carried out in
THF. Ligands H2Le3 and H2Le4 were extracted
using CHCl3 and recrystallised from MeOH at −20
°C in moderate yields (43 and 64% respectively)
[40]. Ligands H2Le5 and H2Le6 were recrystallised
from pentane with poorer yields (27 and 37%
respectively) [105].
Metal Complexes
The dizinc complexes [LZn2IIEt2] (where L = Le3,
Le4, Le5 and Le6)[40, 105] and mixed-metal
complex [Le4AlIIIMe2ZnIIEt] were prepared, using
diethylzinc (and in one case also
trimethylaluminium) to both deprotonate the ligand
and introduce the metal ions[108]. All but one of
these complexes was structurally characterised: the
zinc(II) centres are all in N2C-donor trigonal-planar
t
coordination environments (Figure 29, see also
ip
Section 3). The loss of the characteristic NH proton
resonance at ca. 10.5 ppm on reaction with
diethylzinc (ethane evolved), and the gain of proton
cr
resonances at 0.2–0.8 ppm consistent with the
remaining, zinc-bound, ethyl groups, clearly
confirm the formation of the desired complexes.
us
Polymerisation studies involved reaction of the zinc
catalyst, BnOH and monomer in toluene under
nitrogen for a given temperature and time, followed
by quenching of the reaction (AcOH) and
an
precipitation of the polymer (MeOH). The dizinc
complexes [Le3Zn2IIEt2] and [Le4Zn2IIEt2] were
highly active “living” catalysts for ROP of CL in
the presence of BnOH. Without the alcohol no
reaction occurs. A 1:1 molar ratio of zinc complex
to alcohol gives the highest catalytic activity. The
number-averaged degree of polymerisation (DPn =
Mn /M0) and molecular weight (Mn) of the polymers
were found to be proportional to the
monomer:BnOH molar ratio. The molecular weight
distribution is narrow, which is a “well-known
feature of coordination polymerisation reactions”
[40]. The mixed metal complex [Le4AlIIIMe2ZnIIEt]
shows modest activity, with the resulting polymers
showing relatively narrow polydispersity (1.1–1.8)
[108]. 1H–NMR spectroscopy was used to analyse
the resulting polymers, which had benzyl and
hydroxymethyl end groups. The active catalyst was
determined to be a metal benzyloxide, formed upon
reaction of BnOH with the alkyl metal complex.
Figure 29: Crystal structure of [Le5Zn2IIEt2] (CSD
refcode CEWZIO), redrawn from data obtained from the
CCDC as published in reference [105]. Carbon = Light
grey, Nitrogen = Light Blue and Zinc = Pink.
32
Page 32 of 60
The final subset in this motif (Figure 30) features
21 symmetrical ligands, whereby two diarylamine
units are bridged by imine links to an ortho-
terphenyl subunit (ring A; 20 ligands), or by an
ortho linked benzene group attached to the 4-
position of one of the aryl units (ring B; 6 ligands),
or bridged by both (so 5 are macrocycles).

t
Ligands in the present motif, H2Le7 to H2Le28

ip
(Figure 30), have been designed with the aim of
serving as catalysts for epoxide / CO2
copolymerisation. The activity of such catalysts is

cr
highly dependent on the N-aryl ortho substituents:
too small gives rise to the formation of inactive
tightly bound bimetallic systems; too large and the

us
system cannot form the bimetallic species.
Controlling the nature and extent of interactions
between the metal centres, should give
improvements such as increased activity at low

an
mole ratios and higher turnover numbers.

Ligand Synthesis
Initially a 2,6-dialkyl-4-bromoaniline derivative is
M
protected with benzophenone by a tetraethyl
orthosilicate mediated Schiff base condensation.
These bromo-substituted compounds can then be
lithiated (nBuLi, THF, −78 °C), converted to
d
boronic acids, coupled with 1,2-dibromobenzene
by a Suzuki coupling reaction, and finally Figure 30: Motif E: Acyclic and macrocyclic
te

hydrolysed using acid to yield the corresponding bis(diarylamines) bridged by phenyl (ring B) and/or
substituted 4,4′′-diamino-o-terphenyl. Reaction of ortho- terphenyl (ring A) groups. See Figure 31 for the
this terphenyl with 2,4-pentanedione affords the synthesis of these ligands.
p

desired β-ketoamine, but further reactions to create

larger structures fails [109]. Instead, Schiff base The analogous imine precursors were prepared for
ce

condensation of 2-fluorobenzaldehyde with the
substituted diaminoterphenyl derivatives (73–87%
yields), followed by nucleophilic aromatic
substitution of the fluorinated precursor with
Li(H)NC6H3R’2 (where R3 = H) in THF yields the
Ac
the fluorinated ligands in the same fashion in
similar yields (60–80%) [110]. In contrast to the
non-fluorinated ligands, the synthesis of the
fluorinated ligands was not successful in THF.

However, carrying out the reaction in toluene

desired acyclic bis(anilido-aldimine) compounds resulted in good yields of the desired ligands (60–
(Ring B absent, Figures 30 and 31) in very good 80%).
yields (86-95%) [109].

33

Page 33 of 60

Figure 31: Motif E: General synthesis of acyclic and
macrocyclic ligands H2Le7–28, as well as the failed
synthesis of macrocycles derived from 2,4-pentanedione.
A similar acyclic derivative, H2Le20, could be
produced with the ring coupled at the opposite end
M
(Ring A absent, Figures 30 and 31) [111]. In this
case, the terphenyl is coupled with 1,3-dioxolane-
protected 2-bromobenzaldehyde, catalysed by
Pd(OAc)2 and DPEPhos with KOtBu in toluene.
d
Subsequently the protecting group is removed
using p-toluenesulfonic acid. Finally, the acyclic
te
ligand is prepared by Schiff base condensation with
the hydrochloride salt of 2,6-di-ethylaniline in
EtOH. The precipitated product was neutralised
p
with saturated aqueous NaHCO3, extracted into
toluene. The crude product was then purified by
ce
distillation under reduced pressure and finally
column chromatography through silica in toluene,
yielding the product in good yield (75%).
Ac
The analogous macrocyclic ligands (both rings
present, Figures 30 and 31) can be synthesised by
coupling the diaminoterphenyls with 1,3-
dioxolane-protected bromobenzaldehyde; removal
of the protecting groups; and finally cyclisation by
refluxing the hydrochloride salts of a second
diaminoterphenyl group in EtOH [109]. The
precipitated hydrochloride salt of the macrocycles
can then be neutralised and purified by column
chromatography through silica.
The series of ligands HLe29-e35 with two bidentate
amine imine binding pockets were published in a
patent by Haosheng Li and coworkers (Figure 32):
no synthetic information is provided[112].
t
ip
Figure 32: Motif E: The diarylamine unit is substituted
cr
at the 2-position by an cyclohexyldiimine, producing a
bis-bidentate ligand.
us
Metal Complexes
All complexes derived from ligands H2Le7-28 of this
motif are zinc(II) based, and feature either methyl
or bridging methylsulfinato (SO2Me) singly
an
charged anions[109-111]. In all cases the
diphenylamine NH is deprotonated by reaction with
dimethylzinc(II). For the methyl anion based
complexes, the zinc(II) centre is in a trigonal N2C
coordination environment, whereas for the SO2Me
anion based complexes, the zinc(II) centre has a
tetrahedral N2O2 coordination environment (Figure
33, and see section 3 later).
Quantitative yields of dinuclear methyl-zinc
complexes were obtained on reaction of Me2Zn
with all of the acyclic bis(anilido-aldimine) and
related macrocyclic ligands, except for the
isopropyl substituted which gave mononuclear zinc
complexes. Notably in the 1H−NMR spectrum, the
NH peaks (10 to 11 ppm) completely disappear and
the Zn–CH3 proton signal appears (−0.5 to −1
ppm). Since β-diketiminato alkoxy or acetoxy zinc
complexes are reported to be effective catalysts for
epoxide / CO2 co-polymerisation, attempts were
made to transform the methylzinc complexes into
the corresponding alkoxy (MeOH) or acetoxy
(AcOH) complexes. However, the demetallated
ligands were the main product. Similarly, it is
shown that alkylsulfinato complexes have been
initiators for such copolymerisation reactions. This
is why the methylsulfinato complexes were also
synthesised, by addition of anhydrous SO2 gas to
the methylzinc complexes. The 1H- and 13C−NMR
spectra of the resulting compounds are rather
complex, with multiple signals for the S–CH3 (1 to
2 ppm) and N=CH (8.0 to 8.1 ppm) environments.
This was attributed to isomerism due to the
34
Page 34 of 60
tetrahedral nature of the sulfur atom and the
dizinc(II) bridging-methylsulfinate structure.
M
d
Figure 33: Crystal structures of complexes with bridging
te
methylsulfinato units (top) [Le23Zn2II(SO2Me)2] (CSD
refcode FIWCIY) [109] and (bottom)
[Le24Zn2II(SO2Me)2] • Et2O (CSD refcode NEKTUT)
[110], redrawn from data obtained from the CCDC as
p
published in the respective references. Carbon = Light
grey, Oxygen = Red, Nitrogen = Light Blue, Zinc = Pink,
ce
Sulfur = Yellow and Fluorine = Green.
Related β-diketiminato copolymerisation reactions
were usually carried out in neat monomer with [Zn]
Ac
/ [monomer] = 1:1000, wherein the maximum
attainable TON is limited to ca. 500. Such systems
struggle under low mole ratio conditions since the
active dimeric species is in equilibrium with the
less active monomeric species. Hence the
dimetallic complexes of H2Le7 to H2Le28 (Figure 30)
were tested at a more dilute [Zn] / [cyclohexene
oxide] = 1:580 and showed high activity.
In a patent published by Haosheng Li and
coworkers[112] the ligands HLe29-35 were
complexed with zinc(II) to give [Le29-35Zn2X] (X =
Me, Et, hexamethyldisilylamido). The patent
abstract describes these complexes as effective
catalysts for macrolide ring-opening polymerisation
at room temperature under mild conditions.
2.6 Motif F — Acyclic Carbazole Based Systems
This motif is based on the carbazole framework,
whereby substitution occurs at both the “front” (1-
and 8-positions) and “back” (3- and 6-positions) of
t
carbazole. All of the resulting 16 acyclic ligands
ip
are symmetrical. The front is substituted by oxazole
[113]; or alkyliminomethyl groups [70, 114], where
the alkyl group is an isopropyl group; or a
cr
substituted benzene derivative; or simple phenyl
groups [115] (Figure 34). Roughly 30, one
fifteenth, of the 385 complexes feature this motif, 9
us
of which are structurally characterised.
an
Figure 34: Motif F: Carbazole derivatives (box)
substituted with oxazole, arylimino, alkylimino or phenyl
groups.
The complexes of the oxazole based ligands, HLf1-
HLf4, have been developed for use as catalysts in
asymmetric Nozaki-Hiyama allylation,
methallylation, propargylation, and allenylation
with ee’s ranging from 20–98%. The sterically
demanding phenyl derivative, HLf12, was prepared
in efforts to produce metal complexes with very
low coordination numbers, in order to study the
structure, bonding and reactivity of such
coordinatively and electronically unsaturated
transition-metal complexes. “Pacman” porphyrins,
such as H5Lf10 [116], consisting of two porphyrins
35
Page 35 of 60
linked by a rigid bridging group, have been used in
the areas of catalysis and energy transfer. The
triazole substituted ligand HLf13 was complexed to
copper to form a complex capable of detecting
cyanide. The remaining ligands were synthesised
for academic interest in investigation of the
coordination behaviour with transition metal ions.
Ligand Synthesis
For the first three oxazole-based ligands, HLf1 to
HLf3, the 3,6-phenyl substituents were introduced
by iodination of carbazole using KI (followed by
KIO3) in AcOH [117]; followed by a Pd(OAc)2
catalysed Suzuki coupling of the 3,6-diiodo
derivative with phenylboronic acid in the presence
of Ba(OH)2·8H2O and P(o−tol)3 in DME. The
mixture was then heated, filtered and subsequently
purified by flash chromatography [118]. Then the
oxazole unit was introduced to the 1,8-positions in
three steps: iodination using I2 and HIO4·H2O
successively in a solvent mixture of AcOH / H2O /
H2SO4 and purification by extraction into EtOAc;
secondly, a Pd(PPh)3 catalysed direct amidation of
M
the corresponding diiodo carbazoles (with varying
amines) in DMF in the presence of CO and TEA at
60 °C; and lastly, a BF3·OEt2 mediated oxazoline
formation in refluxing xylene. The other oxazole
d
ligand, HLf4, is similar to that of HLf3 but with tert-
butyl groups in the 3,6 positions [49]. Hence the
te
synthesis of HLf4 started from 3,6-di-tert-butyl-
carbazole, which was brominated in the 1,8-
positions in DMF. Then these bromo groups were
p
converted to nitrile groups with a Rosenmund-von
Braun reaction, and finally oxazole formation was
ce
achieved by addition of phenylglycinol with ZnCl2.
For the imine based ligands, HLf5-HLf11, the
corresponding dialdehydes were synthesised in a
Ac
multi-step procedure [70, 114]. First, the more
reactive 3,6-positions were protected with either
tert-butyl groups by a Friedel–Crafts alkylation, or
with methyl groups by quantitative bromination
using NBS, followed by N -protection, lithiation
and subsequent methylation. These 3,6-substituted
carbazoles were then brominated, using Br2 and
NBS respectively. Lastly, formyl groups are added
by N-protection, lithiation and finally formylation.
The alkyliminomethyl groups were introduced by
Schiff base condensation reactions of the carbazole
dialdehydes with the appropriate amine. This was
facilitated by addition of molecular sieves and/or 5
drops of glacial acetic acid. The imine ligands were
prepared using the conditions in Table 4.
Table 4: Reaction conditions for imine formation to
produce ligands HLf5, HLf6, HLf7 and HLf11.
Ligand Reaction Reflux Recryst. Yield
solvent time from
HLf3 Toluene 16 hr MeCN 96
t
HLf4 EtOH 16 hr Hexane 46
ip
HLf5 CHCl3 3 days EtOH/hexane 70
HLf6 DCM 16 hr N/A 91
The porphyrin-containing imine ligand H5Lf10
cr
required a slightly different synthetic approach
[116]. The nitro porphyrin species was prepared by
reaction of 4-nitrobenzaldehyde with 1,19-dideoxy-
us
8,12-diethyl-2,3,7,13,17,18-hexamethylbiladien-
a,c-dibromide and a catalytic amount of para-
toluenesulfonic acid in EtOH at reflux for 3 days.
an
This intermediate could be purified by column
chromatography through silica in CHCl3, and
isolated in 46% yield. This could be further
purified by recrystallisation from CHCl3/MeOH.
The amino porphyrin was prepared by reduction of
the nitro compounds using SnCl2·2H2O in CHCl3
and HCl in Et2O. This amino substituted porphyrin
could be purified by column chromatography
through silica in 100:5 DCM : MeOH, giving a red
solid in 84% yield. Finally, the ligand H5Lf10 could
be prepared by reaction of the amino porphyrin and
carbazole dialdehyde precursors in degassed
pyridine at reflux for 3 days. This ligand could be
purified by column chromatography through silica
in 100:5 DCM:MeOH, and isolated as a brown
solid in 85% yield. Interestingly, attempts to reduce
the imines using NaBH4 failed, which was
attributed to the C=N bond being highly stabilised
by the ‘aromatic pathway’ of the molecule.
The phenyl substituted ligand HLf12 was prepared
by Suzuki coupling of 1,8-dibromo-3,6-di-methyl-
9H-carbazole precursor (described above) with
phenylboronic acid, using Pd(PPh3)4 in EtOH,
toluene and aqueous Na2CO3 at 80 °C for 16 hrs
[119]. The resulting solution was filtered, washed
and the solvent evaporated. The crude material
could then be recrystallised from hot EtOH/ n-
hexane to give an off-white solid in good yield
(85%) [119].
The two 1,2,3-triazole substituted ligands HLf13 and
HLf14 were synthesised by different groups, using
similar methods [120, 121], starting from 1,8-
36
Page 36 of 60
dibromo-3,6-di-tert-butyl-carbazole. Initially a
TMS or hydroxypropyl protected acetylene group
was introduced through a Sonagashira reaction, and
then deprotected to yield 3,6-di-tert-butyl-1,8-
diethynyl-9H-carbazole. A subsequent 1,3-dipolar
cycloaddition gave the chosen 1,2,3-triazole
groups. The HLf13 ligand features singly N-
alkylated triazoles and was synthesised in 81%
yield by reacting the 1,8-diethynyl carbazole with
benzylazide with copper sulphate and sodium ɛ-
ascorbate in THF at 50 °C for 12 hrs (58% from
1,8-dibromo-3,6-di-tert-butylcarbazole) [121]. The
(HLf13)+ ligand featuring N,N-dialkylated triazoles
was synthesised in 43% yield by reacting the 1,8-
diethynyl carbazole in dry dichloromethane with a
1,3-diaza-2-azoniaallene salt, 1,3-bis(2,6-
diisopropylphenyl)-triazine [120], in the presence
of anhydrous KPF6 and tert-butyl hypochlorite, at -
78 °C in the dark, resulting in the mixed salt [Lf14]
Cl(PF6). The addition of potassium
hexamethyldisilazide to a THF solution of HLf13 at
-78 °C deprotonated the carbazole NH and
facilitated isolation of [Lf13]PF6 as an air and
M
moisture sensitive red solid in 93% yield. Changing
the solvent and using excess base removed the next
most acidic protons, the C-H protons of the two
triazoles, giving the organometallic, neutral dimer
d
[KLf13]2 in 72% yield.
te
The ligands HLf15 and HLf16 contain two different
phosphate groups, either an acyclic diphenyl
phosphate or a cyclic 2,5-diphenyl
p
phospholane[122]. Starting from 1,8-dibromo-3,6-
di-tert-butyl-carbazole, a hydroxymethylene group
ce
was introduced at the 1,8-positions by lithiation
with TMSCl and then further lithiation with
paraformaldehyde. This alcohol group was then
reacted with PBr3 to give the bromomethyl
Ac
compound. This key compound is then reacted with
one of two lithium-phosphorus compounds,
through a borane protection then deprotection.
The ligand, HLf17, used by Kay’s group is
commercially available. The ligand was then
treated with nBuLi in hexane to deprotonate the
amine nitrogen giving LiLf17 [123].
Metal Complexes
For the oxazole based ligand HLf2, the respective
metal complexes are made in situ when the Nozaki-
Hiyama reactions are being investigated [118].
These reactions are mediated by Cr(III)/chiral
ligand, for example, the reaction of silylpropynes
with benzaldehyde was carried out. The same
catalytic procedure was used for the asymmetric
allenylation as for the asymmetric propargylation
and allylation. The following components were
used in these reactions: chiral ligand (10 mol %),
CrCl2 (10 mol %), Mn (2 eq.), various bases (30
mol %; DIPEA, K2CO3, γ-collidine, pyridine) in
t
various solvents (THF, DME, DCM, DMF, MeCN,
ip
EtCN). The silylpropyne and subsequently
benzaldehyde with TMSCl were added and reacted
for 6–48 hrs, giving yields of 49–92% and ee’s of
cr
29–80%. Reaction in propionitrile using DIPEA as
base gave the best results.
us
Niwa and Nakada used ligands HLf3 (carbazole-
based) and HLc18 (diphenylamine-based analogue;
see section on Motif C and Figure 10 above) to
form Fe(III) complexes, with the aim of mimicking
an
the key properties of analogous porphyrin
complexes in order to access catalysts for highly
enantioselective asymmetric epoxidation [49] The
complex of HLf3, [Lf3FeCl2] showed activity for the
conversion of 1,2-diphenyl ethene to 2,3-diphenyl
oxirane at 1 mol% loading with 4 mol% NaBARF
(sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]
borate) and 3 equivalents of PhIO. The yield of this
reaction was improved by addition of SIPrAgCl
(SIPr = N,N′-bis(2,6-diisopropylphenyl)-4,5-
dihydroimidazol-2-ylidene), giving the best result
of 55% yield with 88% ee after 60 minutes.
Following this result, the group extended the study
of [Lf3FeCl2] to other asymmetric epoxidations,
which also showed moderate yields with high
enantiomeric excess.
The bis-oxazolinyl ligand HLf4, was combined with
three transition metal salts to give three complexes,
[Lf4MX] (M = Ni and X = ClO4 or M = Cu, Zn and
X = OTf)[124]. These three complexes were
designed as catalysts for the reaction between
acryloyloxazolidinone and C,N-diphenylnitrone. In
the absence of a catalyst this reaction has four
products, the reaction can yield either a 4- or 5-
substituted isoxazolidine and in both cases either an
exo or endo fashion. Introduction of any of the
three catalysts resulted in only the 4-substituted
isoxazolidine product, with varying ratios of endo
and exo products. The presence of a catalyst also
reduced reaction time from 72 hrs to 48 hrs. The
zinc(II) complex showed low enantioselectivity and
diastereoselectivity, even as the catalyst loading
37
Page 37 of 60
increased from 10 to 20 to 30 mol%. The copper(II)
complex showed improved stereoselectivity over
the zinc(II) complex and also improved at the
catalyst loading increased. Interestingly at 10 and
20 mol% loading the copper(II) complex the ratio
of the endo-isomer is 28-30 %, when the loading is
increased to 30 mol% the diastereoselectivity
switches and you get a ratio of 95% for the endo-

t
isomer. The nickel(II) complex showed strong

ip
selectivity, however unlike the other complexes,
the selectivity is reduced as the catalytic loading is
increased from 10 to 30 mol%.

cr
A range of manganese(II), iron(II), iron(III) and
cobalt(II) complexes of Lf5, Lf6, Lf7 and Lf11 were

us
prepared [70, 114]. Similarly, the complexes
[(Lf12)2MII] (where M = Cr, Mn, Fe and Co) were
prepared (Figure 35) [119]. These Lf12 derived
complexes are thermally stable but highly air-

an
sensitive. The UV-vis spectra are dominated by
intense ligand-based π-π* transitions (up to 81,000
L.mol−1.cm−1) between 200 and 400 nm. The
transitions past 400 nm were assigned as d-d
M
transitions despite their relatively large molar
absorptivity (498–7763 L.mol−1.cm−1). All of these
complexes were paramagnetic, being in the high-
spin state. DFT calculations were carried out and
d
support these findings.
te

Polymerisation studies were carried out using the

iron(II/III) and cobalt(II/III) complexes of Lf5 and
Lf7 and related bis(imino)pyridine, pyrimidine and
p

triazine systems [70]. The study investigated the

polymerisation of ethylene polymerisation at both
ce

low-pressure (Schlenk line, 100 eq. MAO co-
catalyst) and high-pressure (4 bar, 1 L stainless
steel reactor, 1000 eq. MAO). Coordinating (Cl–)
and non-coordinating (SbF–) counterions were
used. All complexes of Lf5 and Lf7 showed neglible
Ac
Figure 35: Crystal structures of complexes (top)
[Lf5FeIIICl2] with trigonal-bipyramidal Fe(III) (CSD
refcode IJAMOV) [114], (middle) [Lf7CoIICl]•C7H8 with
tetrahedral (CSD refcode TADYIH) [70] and (bottom)

[(Lf12)2CoII] with unusual “linear” Co(II) geometry

activity under Schlenk conditions. There are
multiple possible reasons for this result. Perhaps
most importantly is the steric hindrance present at
the active site. Similar aryl substituted
bis(imino)pyridine show polymerisation activity.
The carbazole based ligands have two extra carbon
atoms in the backbone giving an extended “reach”
and thus reducing the availability of the olefin to
coordinate. Furthermore, the central amine on the
carbazole ligands is negatively charged, leading to
neutral (rather than cationic), leading to a much
lower activity.
(CSD refcode AHOHEL) [115] geometries, redrawn
from data obtained from the CCDC as published in the
respective references. Carbon = Light grey, Oxygen =
Red, Nitrogen = Light Blue, Cobalt = Navy Blue
(middle) and Pink (bottom), Iron = Orange and Chlorine
= Green.
The complexes [Lf5CuIIOAc] and [Lf7CuIICl] were
prepared for comparison against the complexes of
H5Lf10 [116]. These two complexes undergo
reversible one electron oxidations at 1.12 and 1.19
V respectively, with the resulting radical cation
being relatively stable (as seen by reversible
nature). These complexes also exhibit an

38

Page 38 of 60
irreversible (even at −70 °C) reduction at −1.05 and
−0.55 V respectively, assigned as Cu(II) → Cu(I).
These reductions have an associated small
oxidation at −0.06 V on the return sweep, assigned
as Cu(I) → Cu(II), but where the copper ions is
either uncomplexed or coordinated by a ClO– anion
from the electrolyte.
The synthesis of the two carbazole-coordinated
complexes [CuII(OAc)Lf10Cu2II], in 98% yield, and
[CuII(OAc)Lf10Zn2], in 64% yield, required slightly
different strategies (Figure 36), starting from the
copper(II) aminophenylporphyrin (CuAPP)
precursor, or the free H5Lf10 ligand or the zinc(II)
bound precursor [HLf10Zn2] [116]. It is worth
noting that in the absence of sodium acetate, the
yield of the [HLf10Zn2] precursor decreased
considerably, which the authors attributed to “acid
attack of the imine bond by protons generated
during the metalation process.” Deprotonation of
the carbazole NH and coordination was achieved
by 10 min reflux with M(OAc)2·xH2O/NaOAc in
MeOH/DCM for M = Cu, but failed for M = Zn.
M
Notably, all complexes derived from H5Lf10
exhibited Soret- and Q-bands, with very intense
transitions of up to 380,000 L.mol−1.cm−1. The
electrochemical properties of these complexes were
d
investigated. In all cyclic voltammograms, one-
electron oxidations of the carbazole moieties were
te
observed, with the subsequent radical cation being
unstable (radical coupling) on the electrochemistry
timescale and resulting in a rapid chemical reaction
p
(shown by absence of a reversible process). In the
CV of [CuII(OAc)Lf10Zn2] there are oxidation
ce
processes at 0.57 and 0.75 V, attributed to the
separate oxidation of each porphyrin. Apparently,
the copper(II) ion enhances π-π interactions
between the two macrocycles. This was supported
Ac
by low-temperature ESR data. This compound also
exhibits an irreversible Cu(II) → Cu(I) reduction at
ca. −1.00 V, assigned based on comparison to
[Lf5CuIIOAc] and based on the changes observed in
the UV-vis spectra. There are two additional
reduction processes at −1.53 and −1.67 V in
[CuII(OAc)Lf10Zn2], attributed to the formation of
the porphyrin π-anion radical. The appearance of
two processes was attributed to one of the zinc
centres picking up the acetate ion, which is rapidly
expelled upon the earlier Cu(II) → Cu(I) reduction,
thereby changing the reduction potential of the
porphyrin rings. This was confirmed with anion
binding experiments, whereby a 1:1 relationship
was established (OAc– and Cl– binding, log K = 3).
Notably, the all copper complex [CuII(OAc)Lf10
Cu2II] exhibits only one porphyrin based reduction
process at −1.50 V. Apparently the acetate anion
binding is specific to the zinc complex, since
acetate does not coordinate strongly to the
copper(II).
t
ip
cr
us
an
Figure 36: Synthetic strategy in the synthesis of
complexes derived from H5Lf10. The complexes matching
the search motif are in enclosed in boxes. Key: ellipse =
carbazole; square = porphyrin.
The CNC-pincer ligand HLf13 synthesised by
Bertand’s group formed two interesting complexes,
a nickel(II) hydride complex and a copper(II)
complex with “see-saw” geometry (see
below).[120] The complex [Lf13NiH] was
synthesised by reaction of HLf13 in THF with
[Ni(DME)Cl2] and KN[Si(CH3)3]2 at -78 °C. The
presence of the coordinated hydride was supported
by a characteristic hydride signal at -6.30 ppm in
the 1H-NMR spectrum, and by the X-ray crystal
structure (see later, Section 3). The complex also
features two nickel-carbene adducts, this
bis(carbene) hydride nickel complex was the first
of its type. Overall the complex has a distorted
square-planar geometry, common for these planar,
pincer ligands. Given the results of the first
complexation, the same reaction was carried out
using CuCl2 as the metal salt. This gave the
complex [Lf13CuIICl] which, by X-ray
crystallography, was shown to have an unusual
“see-saw” geometry with the chloride ion sitting
above the ligand-Cu plane (see section 3). Attempts
were made to displace the chloride ion with a
hydride, however these only yielded the complex
[Lf13CuI] which has a T-shaped geometry.
The di-triazole, pincer ligand HLf14 was synthesised
as a fluorescent detector of cyanide.[121] The
39
Page 39 of 60
ligand itself showed strong UV-vis absorptions
around 300 and 370 nm and fluorescence emission
around 385 nm. The copper(II) complex,
[Lf14CuII(ClO4)], was then prepared and its UV-vis
showed the absorptions were red shifted to 326 and
405 nm and almost complete loss of the
fluorescence emission at around 385 nm. Upon
addition of up to one equivalent of tetra-
butylammonium cyanide (TBACN) absorptions
around 360 and 408 nm increased and no change
was seen around 346 and 405 nm. These changes
were proposed to be due to ligand exchange of
perchlorate for cyanide, this was supported by
MALDI-TOF-MS. Next, addition of excess
TBACN caused the return of the original ligand-
only UV-vis spectrum and the formation of
Cu(CN)2 and Cu(CN)4, the presence of which was
supported by MALDI-TOF-MS. The fluorescent
emission increased slowly and linearly, on gradual
addition of one equivalent of TBACN, and then
rapidly increased to the intensity seen for the free
ligand after addition of 10 equivalents. The
copper(II) complex was tested against a variety of
M
other anions, none of which showed any strong
changes to the UV-vis absorption or fluorescence
emission, showing the strong selectivity of this
complex for cyanide.
d
t
Kay’s group[123] took the lithiated, tetra- Bu-
te
carbazole ligand LiLf17 and reacted it with one
equivalent of ZnCl2 and CdCl2, this gave
[(Lf17)2Zn] and [(Lf17)2Cd]. These complexes were
p
synthesised for structural comparison to known
zincocene complexes. The formation of these
complexes was supported by 1H-, 13C- and 113Cd-
ce
NMR which showed a single ligand proton
environment, no coupling between the cadmium
and ligand carbons and a single resonance in the
113
Ac
Cd-NMR spectrum. X-ray crystallography
showed that both complexes contained no solvent
molecules, likely due to the large steric bulk of the
tert-butyl groups, as well as two different
geometries. The zinc(II) complex has the two
ligands perpendicular while the cadmium(II)
complex has them mirrored (see section 3 for
further crystallographic discussion).
The two PNP, pincer ligands HLf15,16 were used to
form complexes with square-planar d8 nickel(II), as
well as other d8 late transition metal ions.[122]
Many nickel complexes were synthesised with
HLf15, [Lf15NiX] (where X = Cl, Br, H) using
[NiX2(DME)] and nBuLi or [Ni(COD)2]. Multiple
complexes with HLf16 were also formed,
[Lf16Ni(OAc)] using Ni(OAc)2, [LyNiX] (where X
= Cl, Br, H) using [NiX2(DME)] and LDA or
[Ni(COD)2]. Changing between a Cl- and a Br-
coordinating ligand for [Lf15NiX] caused several
structural changes including the position of the
nickel ion relative to the carbazole plane and the
t
Ni-N bond length, proposed to be due to their
ip
relative trans-effects. The complexes of HLf16
showed many similarities to those of HLf15 and all
of the complexes were of distorted square-planar
cr
geometry (see section 3 for further crystallographic
discussion).
us
2.7 Motif G - Macrocyclic Carbazole Based
Systems
This motif is also based on a carbazole framework,
an
with the resulting macrocycles containing either
one or two carbazole moieties, resulting in a
porphyrin-like coordination geometry and donor set
(Figure 37 and see later Figure). Nine different
macrocyclic ligands have been employed. Only
nine of the 385 complexes feature this motif, 3 of
which are structurally characterised.
In the first subset for this motif, three fused
benzene rings are attached to the carbazole moiety,
and the 1- and 8-positions of the carbazole are
substituted by a tripyrrole linker forming a
porphyrin-like macrocycle (Figure 37). These
compounds are termed picenoporphyrins, after the
[5]phenacene structure. Efficient communication
between π-systems of such porphyrin macrocycles
is desirable, especially considering possible
applications such as use in photoelectric devices
and molecular wires or as photosensitive
compounds that facilitate singlet oxygen formation
for use in photodynamic therapy (PDT). Ligands of
this moiety have been produced in efforts to
produce extended π systems.
A variety of metal complexes have been prepared
using this motif, with ligands that are substituted at
the ‘back’ of the extended carbazole unit (Figure
37: H, nPr, Cl, Br or =O) or at the remaining meso-
substitution sites of the porphyrin framework (Ph
or C6H3(tBu)2). The electronic spectra of the
precursor complexes and final complexes have
Soret- and Q-bands in the visible range, and have
40
Page 40 of 60
typical large extinction coefficients (up to 500,000
L.mol-1.cm-1).
The precursor bis-ethynyl porphyrin free-base or
nickel(II) compounds were produced by a
palladium(0) catalysed (10 mol% Pd(PPh3)4)
coupling of the respective bromoporphyrin
precursor [125] with the corresponding alkynyl
trimethylstannanes in refluxing THF [126]. The
crude product could then be purified by column
chromatography through silica using 1:4 toluene :
cyclohexane followed by DCM, or through
activated neutral alumina in 1:1 DCM : hexane in
good to excellent yields (38–93%). The resulting
compounds exhibit a ruffled conformation,
whereby the opposite pyrrole rings are slightly
counter-rotated. Notably, the Ni—NCz bond length
is one of the shortest reported in any nickel(II)
porphyrin crystal structure.
M
d
te
Figure 37: Motif G: Benzo-fused carbazole-based
p
macrocycles.
ce
The nickel(II) complexes of H2Lg1, H2Lg3 and
H2Lg4 were prepared by conversion of the nickel(II)
2,3-dibromo-5,10,15,20-tetraphenylporphyrin
precursor [125] to the acetylene derivatives using
Ac
Pd(PPh3)4 in THF at reflux. Finally, these alkynes
could undergo Bergman cyclisations by refluxing
(190–280 °C) in CB or TCB with 5% CHD for 8–
60 hrs. The products were purified by column
chromatography through silica by elution with 1:4
toluene : cyclohexane followed by DCM.
Recrystallisation was carried out in DCM / MeOH.
The complexes [Lg1NiII] (Figure 38), [Lg3NiII] and
[Lg4NiII] were prepared in 89, 50 and 86% yield
respectively [126]. The metal-free and nickel(II)
containing macrocyclic acetylene precursor to
H2Lg1 could also be cyclised under ambient
conditions in 2:1 CHCl3 : MeOH and DDQ. The
products were purified by column chromatography
through activated neutral alumina in DCM for the
free base (40% yield) and in 3:7 DCM : hexane for
the nickel(II) complex (30% yield) [127]. In these
reactions, two major steps were identified:
Bergman cyclisation with radical addition; and
hydrogen loss with re-aromatisation. The latter step
was found to be rate limiting and required DDQ
(2e– / 2H+ acceptor) for acceptable yields.
t
ip
cr
us
an
Figure 38: Crystal structure of [Lg1NiII] (CSD refcode
QUQYAC), redrawn from data obtained from the CCDC
as published in reference [126]. Carbon = Light grey,
Nitrogen = Light Blue and Nickel = Green.
The bromo- and iodo-alkyne substituted porphyrin
nickel(II) complexes were synthesised as before
and could be thermally cyclised at 190 °C for 6 hrs
in CB and 30-fold CHD, resulting in the complexes
[Lg5NiII] (65%) from the bromo precursor and a
mixture of [Lg1NiII] and [Lg6NiII] (15 and 45%)
from the iodo precursor [128]. These could be
purified by column chromatography through
activated neutral alumina using 1:1 DCM:hexane.
An investigation into reaction conditions for the
cyclisation of these halogenated precursors was
carried out, wherein reaction temperature and
solvent choice was varied. Notably, use of DDQ in
CHCl3 / MeOH under ambient conditions gave
[Lg1NiII] in 30% yield within half an hour.
The metal-free alkyne substituted porphyrins could
be metallated with Zn(OAc)2·2H2O and the
resulting 2,3-dialkynylporphyrins could then be
transformed into the benzoporphyrins derivatives
by a Bergmann cyclisation of the adjacent
acetylene substituents. This could be carried out
under thermal or photo-induced conditions. The
thermal reaction was carried out as above, and the
products purified by column chromatography
through silica in hexane (to remove CB), then 2:1
41
Page 41 of 60
DCM : hexane, and finally recrystallised from
DCM / MeOH in fair to good yields (30–70%). The
photo-induced Bergman cyclisation was carried out
in benzene and isopropanol at 10 °C using visible
light (λ ≥ 395, 515 or 590 nm), and the products
purified by column chromatography through silica
in 1:1 DCM : hexane [129].
1,3,2-dioxaborolane in THF added at −78 °C,
followed by stirring at RT overnight. This mixture
was hydrolysed at 0 °C using aqueous HCl (1 M).
The crude product was purified by recrystallisation
from hot hexane to give a white solid in 50% yield.
This boronic ester substituted carbazole was then
cyclised (a fourfold Suzuki-Miyaura coupling) with
2,6-dibromopyridine using Pd(PPh3)4 and K2CO3 in

t
The complex [Lg7NiII] was prepared in a multistep toluene and EtOH at 85 °C for 17 hrs. The crude

ip
synthesis [130]. The precursor diester is reacted product was filtered through a silica plug in DCM,
with Ni(acac)2, followed by hydrolysis of the impurities removed using GPC and finally purified
diester and subsequent conversion to the diacid by column chromatography in 1:1 hexane : DCM to

cr
chloride and finally cyclised (intramolecular yield the desired [2+2] macrocycle as a white solid
Friedel–Crafts) in benzene using SnCl4. The crude in 15% yield. Notably, the carbazole NH peak is
product contains a mixture of isomers that could be shifted downfield compared to the dibromo

separated by column chromatography through
silica in 1:1 DCM : n-hexane to EtOAc : 0.1%
AcOH, and recrystallised from DCM / MeOH,
yielding the diketone complex [Lg7NiII] in 44%
us
precursor, attributed to hydrogen-bonding, and is in
contrast to porphyrins in which the NH peaks are
shifted significantly upfield due to diamagnetic ring
current.

an
yield [130]. This compound has electronic
transitions between 390–830 nm (ɛ = 11,700–
74,800 L.mol−1.cm−1). Interestingly, the oxygen
atoms from the ketone functionality are in close
M
proximity to one another (2.86 Å) resulting in easy
protonation of the diketone. This conjugated 1,4-
diketone is similar to quinone, supported by
electrochemical experiments [131]. This compound
d
had four one-electron reduction processes (−0.78,
−1.17, −1.73 and −2.18 V vs Fc/Fc+) and two one-
te

electron oxidation processes (0.70 and 1.12 V).

In the second subset within this motif, two

p

carbazole units are bridged by pyridine, again

forming a porphyrin-like macrocycle. Such
ce

porphyrin derivatives have been extensively

studied due to their biological relevance and ability
to coordinate to a range of metal ions. They have
many other properties including photo-, chemical- Figure 39: Macrocycle containing two carbazole
Ac

and thermal-stability, and a variety of applications moieties.

including catalysis, organic electronics, NLO and
PDT. To this end Müllen and co-workers have
prepared the symmetrical dicarbazole macrocycle
H2Lg8 (Figure 39)[132].
Ligand Synthesis
The ligand H2Lg8 is prepared in a two step synthesis
[132]. The dibromo precursor is protected in situ by
first deprotonating / lithiating using nBuLi in THF
at 0 °C, followed by N-protection by bubbling CO2
gas through the solution for half an hour at RT.
This protected species could then be borylated
using tBuLi and 2-isopropoxy-4,4,5,5-tetramethyl-
Metal Complexes
The complex [Lg8CoII] was prepared and could be
monitored by 1H–NMR spectroscopy (in DMF-d7)
at 130 °C, wherein the macrocycle peaks
disappeared and new, broad peaks appeared and are
highly shifted, as the product is a paramagnetic
species[132]. The NH stretching vibration at 3487
cm−1 disappears on complexation. This complex
was assigned as being high spin cobalt(II) on the
basis of XPS data. UV-vis transitions at 331 and

42

Page 42 of 60

425 nm (ɛ ∼21,000 and 13,000 L.mol−1.cm−1)
were assigned as MLCT. The free macrocycle
emits at 402 nm (φ = 0.36), which is quenched
upon complexation. CVs of the ligand showed two
irreversible oxidations (ca. 1.35 and 1.55 V)
attributed to each carbazole moiety being oxidised
(i.e. radical cation at each carbazole). In contrast,
the complex showed two reversible oxidations
(0.78 and 1.05 V), attributed to one metal based
(CoII → CoIII) and one ligand based (L → L·+)
oxidation.
In a patent by Higashimura and Koshino the
ligands H2Lg8,9 and the cobalt(II) complexes,
[Lg8,9CoII], are listed as compounds for use as
positive electrode catalysts for air secondary
batteries[133]. This catalyst is described as highly
active in both oxygen reduction and H2O oxidation.
In a second patent[134] the complex [Lg8CoII] is
M
listed as a compound used in fuel cell electrodes.
2.8 Motif H — Extended Porphyrins
d
This motif contains fused porphyrin derivatives, in
particular “T”- and “L”-shaped porphyrin tapes and
te
tetraporphyrin sheets (Figures 40 and 41) and
“tetra-porphyrin” derivatives (Figure 42). There is
one example of an anthracene fused porphyrin
derivative (Figure 43). These seven macrocyclic
p
ligands have been used to date to generate seven
complexes with Motif H, only one of which is
ce
structurally characterised. These materials have
extended π-conjugation over the entire flat
molecule. The large π system suggests they should
have unusual optoelectronic properties.
Ac
Figure 40: Motif H: T-shaped fused porphyrin
derivatives.
The T- and L-shaped porphyrin tapes (Figures 40
and 41) are constructed from 5-, 10- and/or 15-
substituted porphyrin units fused together [135].
These compounds have been investigated for their
t
optical behaviour, in particular two-photon
ip
absorption in relation to the molecular shape. Such
behaviour can be useful for applications such as 3D
micro-fabrication, optical storage, optical-limiting
cr
devices and PDT. The “tetra-porphyrin” has four
5,10-substituted porphyrin units fused together.
There is one example of a metal complex of this
us
type: a tetrazinc complexes with 3,5-di-tert-
butylbenzene substituents along the edges of the
framework [136, 137]. Porphyrin systems have an
electronic network suited for use in host-guest
an
chemistry, particularly for identifying organic
molecules or biomolecules bound to the central
metal in the porphyrin. Consequently,
complexation studies of organic molecules to this
system in solution have used 1H−NMR
spectroscopy and DFT calculations. Related meso-
meso coupled porphyrin systems, for which the
diarylamine unit is no longer present, have been
investigated for their use as optical molecular wires
capable of transmitting captured excitation energy
over a long distance [138].
Figure 41: Motif H: L-shaped fused porphyrin
derivatives.
The T- and L-shaped porphyrin tapes were
prepared by reacting “core porphyrin segments”
with “side porphyrin segments” [135]. Long alkyl
meso-R groups were chosen to circumvent steric
43
Page 43 of 60
interactions and improve solubility. The ligands
(H8Lh1–2 and H6Lh3–4) could be prepared by Suzuki-
Miyaura coupling of borylated core- and
brominated side-porphyrins using Pd2(dba)3·CHCl3,
PPh3, Cs2CO3 and CsF (in 2:3 toluene : DMF) at
100 °C under Ar. The resulting meso-meso coupled
porphyrin intermediates were purified by
preparative GPC-HPLC in variable yield (20–

t
57%), which could then be metallated using

ip
Zn(OAc)2 (in MeOH / CHCl3) at 50–60 °C. The tri-
and tetra-zinc complexes could be purified by
column chromatography through silica followed by

cr
recrystallisation. The final step to produce the
complexes [Lh1–2Zn4] and [Lh3–4Zn3] was oxidative
ring closure of the meso-meso linked oligomers

us
using DDQ and Sc(OTf )3 (in toluene) at 90 °C
under Ar. The crude products were purified by
column chromatography through alumina in THF,
followed by recrystallisation from DCM / MeCN,

and were isolated in good yield (70–89%).
In all solution state studies of the porphyrin tapes
[Lh1–2Zn4II] and [Lh3–4Zn3II], n-butylamine was
M
added to coordinate to the axial sites of the zinc
centres in order to suppress aggregation [135].
These porphyrin tapes absorb extensively
throughout the UV-vis and into the infrared region
d
having moderately intense absorption (Soret and Q)
bands up to 184,000 L.mol−1.cm−1. The 1H−NMR
te
an
Figure 42: Motif H: “Tetra-porphyrin” derivative.
The tetrazinc tetraporphyrin sheet [Lh6Zn4II] is
synthesised by a stepwise coupling reaction
sequence, thereby joining four 5,10-diaryl
substituted monometallic (Zn) porphyrin rings
together [136, 139]. This was achieved in three
steps. The first is the coupling of two of these
monometallic complexes, producing a mixture of
the dimers, trimers and tetramers. This was carried

spectrum of this ligand is consistent with D4h

symmetry. Interestingly, this spectrum also exhibits out by addition of AgPF6 (in MeCN) to a solution
two pyrrole NH peaks (13.32 and 12.23 ppm), one of this monomer (in CHCl3) at 5 °C. The dimers
were separated from the rest by preparative GPC-
p

with long range coupling to the corner pyrrole β-

protons, excluding the alternative symmetric HPLC in 24% yield. This racemic mixture of the
dimer was then coupled using the same conditions
ce

tautomer. Notably, the pyrrole NH protons are

considerably deshielded, whereas other porphyrins
have significantly shielded NH protons due to ring
currents. DFT calculations (GIAO-B3LYP/6-31G*
Ac
to yield a mixture of isomers of the tetramer in 40%
yield. The final step, using this mixture, flattens the
meso-meso linked system, forming nine new bonds
under stronger oxidative conditions of Sc(OTf )3

level) were carried out and demonstrate the strong

anti-aromatic nature of the central and DDQ in toluene at 100 °C under an argon
cyclooctatetraene (COT) core. This was confirmed atmosphere [139]. Column chromatography
experimentally by coordination of 1,4-bis(1- through alumina eluting with THF was used to
methylimidazol-2-ylethynyl)benzene to the purify the black product. This material was finally
tetrazinc complex, wherein the 1,4-phenylene recrystallised from DCM / MeCN, yielding the
protons were shifted downfield by 3.78 ppm due to fully π conjugated porphyrin array in 30% yield for
being in close proximity to the COT core [136]. that step. The free base H8Lh6 could be prepared by
demetallation using TFA / H2SO4 (in CHCl3) at 0
°C under a nitrogen atmosphere [139]. The tetra-
copper(II) complex could then be produced by
reaction of the free base (in CHCl3) with Cu(OAc)2
(in MeOH) at reflux under nitrogen. The
compounds H8Lh6, [Lh6Zn4II] and [Lh6Cu4II] could
be recrystallised from DCM / MeCN.

44

Page 44 of 60
Pure 1:2 and 2:4 stable host-guest complexes of
[Lh6 Zn4II] could be produced by addition of excess
amounts of the guest molecules to the tetrazinc
compound (in CHCl3), followed by dilution with
MeCN and subsequent precipitation by slow
evaporation [137]. Two-photon absorption cross-
section values (σ(2)) were established using open

t
aperture Z-scan measurements using femto-second

ip
laser pulse excitation at 2,300 nm. At this
wavelength, in these complexes, ground-state
absorption contributions to the two-photon

cr
absorption cross-section values are negligible. The
tetraporphyrin [Lh6Zn4II] exhibits a relatively small
σ(2) value of 2,750 GM, whereas the T- and L- Figure 43: Anthracene fused porphyrin, H2Lh7.

us
shaped porphyrin tapes, [Lh1Zn4II] and [Lh3Zn3II]
had values of 35,700 and 8,700 GM respectively. A The complex of interest, [Lh7NiII], is synthesised in
variable-temperature magnetic susceptibility two steps from this ligand precursor. The first step
h6 II
measurement of [L Cu4 ] exhibits a steep drop-off is metallation using Ni(acac)2 in m-xylene at reflux

of χT below 20 K, indicative of antiferromagnetic
coupling (J = 1.16 cm−1, g = 2.109). This was also
supported by the powder ESR spectrum.
M
In the anthracene fused porphyrin H2Lh7 (Figure
43), bulky mesityl ether linkages were used at the
edge of the expanded porphyrin to prevent
aggregation, and thereby simplify purification and
d
characterisation [140]. The synthesis of this ligand
requires many steps. The substituted anthrone
te
an
under nitrogen for 3 hrs. This complex could be
purified by filtration through a silica plug in DCM,
followed by precipitation from DCM / MeOH, as
an orange-red product in 84% yield. The final step
in the formation of [Lh7NiII] is the eightfold
oxidative ring closure using excess FeCl3 in DCM
and NO2Me at RT for 30 min. This complex was
purified by column chromatography through silica
in 1:1 PE : DCM with 5% TEA, followed by
precipitation from DCM / MeOH and then DCM /
pentane, as a blue green solid in 49% yield. X-ray

precursor was brominated using PBr3 at 110 °C for

1 hr under a nitrogen atmosphere. This intermediate quality crystals could be grown by EtOH vapour
could be purified by column chromatography diffusion into a benzene solution of [Lh7NiII].
p

through silica in toluene, as a yellow solid in 79%

yield. This could then be lithiated using nBuLi in
ce

Et2O at RT for 25 min and then reacted with 2-

formylpyrrole for 1 hr. The resulting alcohol was
tetramerised in propionic acid and toluene at 100
°C for 3 hrs. This precursor could be purified by
Ac

filtration through a silica plug in CHCl3, followed

by size exclusion chromatography in THF, and
finally precipitated from DCM / MeOH as a red-
brown solid in 10% yield. Notably, this precursor
exhibits very intense UV-vis transitions between
430–648 nm (up to 234,000 L.mol−1.cm−1).

Figure 44: Crystal structure of [Lh7NiII], redrawn from

data obtained from the ESI as published in reference
[140]. Carbon = Light grey, Oxygen = Red, Nitrogen =
Light Blue and Nickel = Green.

45

Page 45 of 60
The uncyclised complexes (before eight-fold ring
closure) also exhibit multiple UV-vis transitions
between 427–564 nm (up to 295,000 L.mol−1.cm−1)
[140]. The cyclised product, [Lh7NiII] exhibits
several additional bands, some featuring a
significant red-shift, between 313–1,417 nm (up to
120,000 L.mol−1.cm−1). The low energy transition
at 1,417 nm is attributed to the HOMO-LUMO
transition (0.87 eV). This complex is expectedly
readily oxidised at just −0.44 V. Consequently,
NMR spectra had to be run in the presence of a
reducing agent (NaBH4) so as to prevent formation
of paramagnetic radical cations. The first reduction
process occurs at −1.05 V. There are several other
processes that have not been assigned.
2.9 Motif I — Acridines and Phenoxazines
This motif features a one atom bridge between the
diarylamine unit at the 6- and 6′-positions (Figure
45). The first ligand that matches this motif is
based on acridine, having two further benzene rings
fused to one side. Only one complex of this ligand
M
has been reported [141]. The second ligand is
bridged by an oxygen atom at the 6- and 6’-
positions of the diarylamine unit. This molecule is
heavily substituted and has multiple possible
d
binding sites. Only two complexes of this second
ligand have been reported [142].
te
p
ce
Ac
Figure 45: Motif I: Acridine and phenoxazine
derivatives.
The metal chelate complex using HLi1 has been
developed as the fluorescent substance layer for
electroluminescent devices, having electron
transport properties [141]. Devices constructed
from these materials had high luminous efficiencies
and intensities, were stable to heat and current and
required low driving voltages. Applications include
flat-panel displays (such as TV’s) or use as plane
light emitting sources (for use in printers, copiers
etc.).
Ligand HLi2 is also known as the cytostatic drug
actinomycin D (AD), the first antibiotic shown to
have anti-cancer activity [143]. This drug acts by
occupying the RNA polymerase binding site; also
inducing physical alterations within the nucleic
acid structure. In the paper of interest [142], the
interaction with plasmid DNA was considered. It
t
was found that the drug itself exhibited no tendency
ip
to alter the DNA structure. However, addition of
copper(II) ions resulted in pH-dependent plasmid
DNA cleavage, even at low concentrations. The
cr
authors concluded the coordination of copper(II)
ions to AD in vivo may be partially responsible for
the numerous adverse effects induced by the drug.
us
2.10 Motif J — Dibenzoazepines
This moiety is based on an alkylamino N-
an
substituted dibenzoazepine derivative, where the
diaryl-amine unit is bridged at the 6- and 6′-
positions by an ethylene bridge (Figure 46). By
definition, the diphenylamine moiety in this motif
is a neutral N-donor. Only two ligands, Lj1 and Lj2,
both with a potentially bidentate propylamino
group, have been complexed with 3d TMs to date.
A number of studies have indicated that
biologically active compounds may have increased
bacteriostatic and carcinostatic properties upon
chelation. Ligands Lj1 (Desipramine, antidepressant
drug) and Lj2 and various metal complexes of them
were investigated for their antimicrobial activity
[144]. Sixteen of the 385 complexes feature ligands
from this motif, none of which have been
structurally characterised.
Figure 46: Motif J: Dibenzoazepine derivatives.
The eleven complexes [Lj1MIIX2(H2O)2], where M
= Cu (X = Cl–, OAc–), Co (X = Cl–, Br–, OAc–, NO–
, ClO–), Ni (X = Cl–, Br–, OAc–) and Mn (X = Cl–),
46
Page 46 of 60
were prepared [144]. All complexes were insoluble
in water and common organic solvents, but readily
soluble in DMF and DMSO. All complexes were
assigned to be high spin, with both amines
coordinating and forming distorted octahedral
geometries. The electronic transitions were
analysed for the complexes derived from Lj1 as
seen in Table 5.
Of the 385 complexes identified in this search, 96
have been structurally characterised (Tables 6-8,
Figures 47-50). Interestingly, no complexes
featuring Motifs I or J; and only one structure for
each of Motifs A (cif unavailable) and H; three for
Motif G; eight for motif B, and nine for each of
Motifs D and F have been structurally

t
characterised. The remaining 65 structures belong

ip
Table 5: UV-vis transitions and assignments for the to Motifs C (51 structures) and E (14 structures).
copper(II), nickel(II), cobalt(II) and manganese(II)
complexes of Lj1. Solvent: DMF.

cr
Transition
Metal (nm) Assignment
2
B1g → 2A1g

us
copper(II) 885-975
2
B1g → 2B2g
2
435-545 B1g → 2Eg
3
nickel(II) 610-780 A2g → 3T1g

an
3
A2g → 3T1g
4
cobalt(II) 685-695 T1g → 4T2g
4
675 T1g → 2A2g
4
608 T1g → 4T2g Figure 47: Pie chart representation of the distribution of
6
A1g → 4T1g the 385 complexes reviewed herein, across the 10 motifs
M
manganese(II) 720-755
590-630 6
A1g → 4T2g identified (Figure 2). See Figure 48 for the distribution
6 for the 96 structurally characterised complexes.
450-465 A1g → 4A1g

Lj1 and complexes were tested against the bacteria

d

E. coli, S. aureus, P. aerugenosa and B. subtilius.

Lj1 and complexes were tested against the fungal
te

strains A. flavus and A. niger. The metal complexes

had two to three times the potency against these
bacteria and fungi compared to the ligand, but were
p

less effective than the standards Chlorampenicol

and Griseofulvin respectively. The nature of the
ce

other coordinated co-ligands was found to have a

significant role in antibacterial/anti-fungal activity,
Figure 48: Pie chart representation of the distribution of
with the acetate complex exhibiting the highest the 96 structurally characterised complexes in the CSD,
potency.
Ac

reviewed herein, across the 10 motifs identified (Figure

Ligand Lj2 also exhibits antimicrobial activity that
is enhanced upon coordination to cobalt(II) [145].
All five of the metal complexes of this ligand are of
cobalt(II), differing only in the counter anions
(ClO4–, NCS–, OAc–, NO3– and SO2–). In these
complexes the ligand was similarly assigned as
being bidentate, where the resulting complexes had
octahedral coordination environments with water
molecules completing the coordination sphere.
Since we could not access this journal no ligand or
metal complex synthesis can be commented on.
3. Structural comparisons
2). See previous figure for distribution across all 386
complexes identified.
Three quarters of these structurally characterised
complexes feature metal ions in the +2 oxidation
state. The 22 exceptions are 4 Cu(I), 2 Ni(I), 8
Fe(III), 2 Cr(III) and 6 Ti(IV) complexes. Most of
the complexes are mononuclear (77), with all but
one of the remainder being dinuclear (18). Just one
is greater than dinuclear, and it is hexanuclear.
The majority of these structures feature the more
geometrically flexible metal ions (Figure 50), zinc
(27 structures) and copper (20 structures), with the

47

Page 47 of 60
remaining 49 structures containing nickel (23
structures), iron (11 structures), cobalt (6
structures), titanium (6 structures), chromium (2
structures) and manganese (1 structure). Of the
three metal ions that predominate, all of the zinc,
and most of the copper and nickel, complexes are
in the +2 oxidation state, but for copper and nickel
there are also a few examples of the +1 oxidation
states being observed. Specifically, of the 20
structures involving copper, Motifs C (2), E (1) and
F (1) give a total of 4 examples of the +1 oxidation
state. Of the 23 nickel structures, Motif C gives 2
examples of the +1 oxidation state, with this
relatively uncommon oxidation state of nickel
stabilized by use of an N2P donor ligand.
M
Figure 49: Pie chart representation of the distribution of
d
metal ions (regardless of oxidation state) within the 385
complexes reviewed. See next figure for distribution
across the 96 structurally characterised complexes.
te
p
ce
Ac
Figure 50: Pie chart representation of the distribution of
metal ions (regardless of oxidation state) within the 96
structurally characterised complexes in the CSD. See
previous figure for distribution across all 385 complexes
reviewed.
The structures of the 96 complexes are discussed
by Motif (A-J) in turn below. As the cif is
unavailable for the only example of a structurally
characterised complex of Motif A, this is not
commented on further herein.
The triarylamine-based Motif B comprises
complexes of only one ligand, 2,2′,2′′-
nitrilotribenzoic acid. In all eight structurally
characterised complexes within this motif, the three
carboxylate substituents on the tripodal ligand are
bound to the metal ion, resulting overall in a
pentadentate NO4 coordination sphere. In all but
one of the eight structures the 3d metal ion has a
five-coordinate, NO4 coordination environment,
with a geometry generally closer to trigonal
t
bipyramidal than to square pyramidal [range 0.44–
ip
1.0 (average 0.70) D3h : C4v]. The remaining
structure features the same pentadentate binding by
the triarylamine ligand, but water provides a sixth
cr
donor, resulting in octahedral NO5 coordinated
nickel(II) centres. The M—NTPA bond distances,
where NTPA is the central amine in the
us
triphenylamine unit, in these structures are
significantly longer than the M—NDPA and M—NCz
motifs in this review. This is attributed to the amine
being a neutral donor and having partial π-bond
an
character due to conjugation with the phenyl rings,
making it only weakly basic and hence poorly
coordinating.
Within the 75 diphenylamine derived structures
[Motifs A (1), C (51), D (9) and E (14), Table 8],
the phenyl rings are twisted away from one another
in order to accommodate the substituents at the 6-
and 6′-positions. This is termed the phenyl twist
angle and the observed range within these
structures is 40.45–89.89°, with an average of
76.52°.
The 51 structurally characterised complexes within
Motif C feature 28 ligands and fall into three
categories: imine-, thiazole- or oxazole-substituted.
The imine based complexes are coordinated to the
metal ion through the central de-protonated amine
and the imine nitrogen atoms. The four-coordinate
metal complexes of these ligands are either very
close to tetrahedral or very close to square planar.
There are two examples of six-coordinate
complexes derived from these ligands, these being
chromium(III) complexes with two trans-
coordinated chloride ligands and two molecules of
THF completing the coordination sphere. The
remaining structures incorporating such imine
ligands, are either trigonally bound copper(I),
nickel(I) and zinc complexes (having acetonitrile,
triphenylphosphine or ethyl co-ligands), and one
copper(II) complex with a chloride co-ligand or
five coordinate titanium(II) complex with
dichloride co-ligands. The M—NDPA bond lengths
in these structures are quite similar (1.935 ± 0.085
48
Page 48 of 60
Å), where NDPA is the central deprotonated amine
in the diphenylamine unit. The remaining structures
in this motif incorporate either oxazole and/or
thiazole based ligands, wherein an atom from the
oxazole/thiazole ring(s) and the central amine
nitrogen atom are coordinated. This results in one
or two six-membered chelate rings which each
impose almost 90° coordination angles. Three of
the structures in this subset are five-coordinate,
being quite geometrically distorted and somewhere
between square-pyramidal and trigonal-
bipyramidal coordination geometries (0.10, 0.83
and 0.67 C4v:D3h). One is a rare example of the
secondary amine in the diphenylamine unit being
non-deprotonated, and is thus very weakly
coordinated to the cobalt(II) ion (M—NDPA = 2.334
Å). The remaining ten structures have a variety of
twist angles (68 ± 22°) similar to the complexes
derived from imine-substituted ligands. Two of
these oxazole/thiazole-based complexes are five-
coordinate iron(III) complexes with two
coordinating chloride ions. There are seven
oxazole/thiazole-based complexes which are four-
M
coordinate nickel(II) complexes, with the
respective co-ligand (Me, CF3, PPh3 or Ph)
coordinated in a mildly distorted square planar
arrangement (0.04–0.33 Td :D4h), and have very
d
similar M—NDPA bond distances (1.93 ± 0.02 Å).
There are nine structurally characterised complexes
te
in Motif D (Table 8). One of these complexes is a
seven coordinate cobalt(II) complex. This system
has a slightly higher M—NDPA bond length
p
compared to the other diphenylamine complexes.
Presumably this is due to the metal centre being
ce
bound to seven nitrogen donor atoms. Given there
are no alkyl substituents at the 6- and 6′-positions
of the diphenylamine unit (as for Motif C) the
phenyl twist angle might be expected to be lower
Ac
than the 76.07° observed, as there are less steric
interactions and since a more acute angle would
lead to an increased degree of conjugation between
the phenyl rings. The remaining eight complexes
feature [1+1] or [2+2] macrocyclic ligands giving
mono- and di-nuclear complexes respectively. The
four dinuclear complexes all feature two copper(II)
atoms with very similar structure, the main
difference being the length of the alkyl chain used
in the diamine. These four complexes have very
similar Cu-NDPA bond distances (1.931 ± 0.008 Å)
and twist angles (57 ± 4°). The geometry of these
complexes is a distorted square planar geometry
(0.27-0.41 Td:D4h). The final four complexes
feature the same [1+1] ligand with either nickel(II),
zinc(II), copper(II) or iron(III). The nickel(II) and
copper(II) complexes contain a tetrafluoroborate
counterion while the zinc(II) complex has a
pyridine co-ligand and a tetraflouroborate
counterion and the iron(III) complex contains two
thiocyanate co-ligands. The twist angles of these
compounds are all similar (50 ± 3°). Due to the
t
rigid nature of the ligands the geometries of these
ip
complexes are either square planar for the nickel(II)
and copper(II) complexes (0.00 and 0.07 Td:D4h),
heavily distorted trigonal bipyramidal for the
cr
zinc(II) complex (0.55 C4v:D3h) or octahedral for
iron(III) complex.
us
Motif E has two diphenylamine units connected
directly or by some bridging unit. Within this
motif, the phenyl twist angles and M—NDPA bond
lengths of the 14 structures (of 8 ligands) are in the
an
ranges 77 ± 13° and 2.02 ± 0.14 Å respectively,
excluding the one non-deprotonated copper(I)
example. As mentioned earlier, this results in
significantly weaker coordination and a
significantly longer M—NDPA bond length. All of
the structures within this motif where the bridging
group is an alkyl chain or a phenyl ring are
dimetallic complexes containing zinc. The zinc
centres are in a trigonal N2C coordination geometry
in the complexes featuring alkyl-substituted
ligands, and almost perfect tetrahedral N2O2
coordination geometries (0.94–0.98 Td:D4h) for the
complexes featuring phenyl-substituted ligands.
The tetrahedral complexes have two
methylsulfinato (µ) bridges. The three iron
structures with a pyridine bridge between the
diphenylamine units are also four coordinate, but
have unusual coordination geometries closest to
trigonal monopyramidal. This is due to the mesityl
rings imposing a large amount of steric bulk,
precluding additional donors in the basal plane
from coordinating. The bond lengths are consistent
with low-spin iron(II) and iron(III) (1.883–1.932
Å). There are also three titanium structures with a
pyridine bridge between the two diphenylamine
units. These complexes feature the same ligand but
with varying co-ligands (NMe2, Cl2 and Cl2/THF)
giving heavily distorted square-pyramidal
geometries (0.48 and 0.30 C4v:D3h) for the two five-
coordinate complexes and octahedral for the six
coordinate complex.
Of the nine structurally characterized complexes of
Motif F two of the structures are reported as two-
49
Page 49 of 60
coordinate, linear manganese(II) and iron(II)
compounds, having N—M—N angles of 178.56(6)
and 177.92(9)° respectively. These complexes
appear to be stabilised by the π-cloud of the nearby
phenyl substituents. The M—NCz bond lengths are
typical for MnII —N and low spin FeII —N bond
lengths. The two carbazole moieties coordinated in
each complex are almost perpendicular (87.92 and
bond length in the nickel(II) complex is the second
shortest of all of the complexes in this review. The
third complex is derived from a bis-carbazole
macrocycle, which is puckered in both the free base
and in the cobalt(II) complex, resulting in a
“saddle-like” conformation that changes very little
upon complexation. This macrocycle provides four
side-by-side six-membered chelate rings, which

t
87.76°). The remaining seven; iron(III), cobalt(II), results in N—M—N angles very close to 90° (90 ±

ip
nickel(II), zinc(II), copper(II) and copper(I) 1°). The incorporation of two molecules of solvent
complexes have oxazole, triazole or imine results in an almost perfect octahedral geometry.
functionality attached at the 1- and 8-positions. In

cr
all seven of these complexes the carbazole-based There is only one structurally characterised
ligand provides two side-by-side six-membered complex featuring a ligand from Motif H,
chelate rings, which have N—M—N angles very [Lh7Ni(II)]. In this structure, molecules form π-

close to 90°. These groups deviate little from the
mean plane of the carbazole unit, 0.001–0.366 Å.
The cobalt(II) complex is in an N3Cl coordination
environment, and has a severely distorted and
us
stacked dimers, separated by ca. 3.4 Å, and rotated
by ca. 20° relative to one another, forming short
Ni···Ni interaction (3.316 Å). The mean deviation
from planarity in the porphyrin core is 0.20 Å.

an
flattened tetrahedral geometry. The cobalt ion sits These dimer pairs dissociate in solution (see
0.35 Å above the pyrrole ring plane of the earlier). The bond lengths are similar to the other
carbazole moiety. The iron(III) complex with an structures, 1.92 ± 0.02 Å. This ligand has a four
oxazole ligand is very similar having just an side-by-side six-membered chelate rings, producing
M
additional bound chloride anion and producing an almost perfect 90° angles (90 ± 2°).
almost perfect trigonal-bipyramidal geometry. The
second iron(III) complex shows very similar
geometry and M-Ncz bond lengths as the other
d
iron(III) complex, however the steric demands of
this ligand cause the donor atoms to sit slightly out
te

of the Cz plane (0.339 and 0.085 Å). The zinc(II)

centre is coordinated to two ligands, resulting in an
octahedral coordination geometry with the
p

carbazole units being not quite orthogonal (78.3°).

Finally there are three complexes which feature the
ce

same triazole ligand and the same NC2X donor set

(X=absent, Cl or H). The copper(II) complex has a
single chloride co-ligand giving a distorted
tetrahedral geometry (0.65 Td:D4h). The copper(I)
Ac

analogue has no co-ligand and has heavily distorted

trigonal geometry due to the rigid ligand. A
nickel(II) complex was also prepared with this
ligand and produced a complex with a Ni-H bond.
This complex was square planar with a Ni-H bond
length of 1.452 Å.

There are three structurally characterised

complexes derived from a porphyrin-like ligand
from motif G. Two of these are benzo-fused
carbazole derivatives of nickel(II) and zinc(II),
which provide almost perfect square-planar N4
environments. The nitrogen atoms of the pyrrole
groups deviate a small amount from the mean plane
of the carbazole (0.393–0.661 Å). The M—NCz

50

Page 50 of 60
Table 6: Selected structural information for the 96 compounds in this review for which crystal structures were reported.

Motif A Fragment of interest Twist angle Geometry Donor set M-NBPA

[NiII(La15 )(PPh 3 ) Ni(II)-NCOP
ref[37] N/A N/A 1.942
(2-tolyl)] (6)

Donor set

t
Motif B Geometry (chelate ring M-NTPA

ip
sizes)
Ni(II)-NO5
FEHGEF[31] (NHEt 3 )2 [L b1 4Ni 6 (OH) 2(OH2 )2 ] octahedral 2.199,2.247
(666)

cr
Cu(II)-NO4
HAHKAD[32] (NHEt 3 )2 [L b1 Cu]2 0.66 C 4v:D3h 2.092
(666)
0.44,0.48,0.71,0.60, Cu(II)-NO4 2.056,2.061,2.069,
HAHKEH[32] [Cu(OH2 ) 4] 3[L b1Cu(OH2)]6
0.60,0.59 C 4v:D3h (666) 2.071,2.081,2.096

us
Ni(II)-NO4
HAHKIL[32] (NHEt 3 )3 [L b1 NiII]2 ClO4 0.66,0.62 C 4v:D3h 2.164,2.176
(666)
Co(II)-NO4
HAHKOR[32] [Co(OH2 ) 6][L 1b Co(OH)] 1.00 C 4v:D3h 2.261
(666)

an
Zn(II)-NO4
HAHKUX[32] [Zn(OH2) 6][L 1b Zn(OH)] 1.00 C 4v:D3h 2.327
(666)
Fe(III)-NO4
HAHLEI[32] (NHEt 3 )2 [(L 1bFe) 2O] 1.07 C 4v:D3h 2.561
(666)
Fe(II)-NO4
ILIZOS[38] (NHEt 3 )2 [L b1 Fe] 2 0.69 C 4v:D3h 2.430
M
(666)

Motif C Twist angle Geometry Donor set M-NBPA

QIFFES[43] [L c3Zn(N(SiMe 3) 2)] 89.83 trigonal Zn(II)-N3 1.915
MICTID[146] [L c3Ni(PPh 3)] 46.86 0.33 Td:D4h Ni(II)-N2 CP 1.920
d

MICTOJ[146] [L c4Ni(PPh 3)] 48.45 0.31 Td:D4h Ni(II)-N2 CP 1.914

QIFFIW[43] [L c5Zn(N(SiMe 3) 2)] 82.32 trigonal Zn(II)-N3 1.913
te

MICTUP[146] [L c5Ni(PPh 3)] 49.89 0.33 Td:D4h Ni(II)-N2 CP 1.918

MICVAX[146] [L c6Ni(PPh 3)] 59.15 0.14 Td:D4h Ni(II)-N2 CP 1.908
RAKTAA[46] [L cxFeCl2 ] 62.25 0.10 C 4v:D3h Fe(III)-N3Cl2 1.989
p

BIDLIL[57] [L c38 ZnEt] 84.35 trigonal Zn(II)-N2C 1.938

BIDLOR[57] [L c38 Zn(OBn)] 2 78.71 trigonal Zn(II)-N2O 1.959
[(L c38 )2 Zn]
ce

BIDLUX[57] 83.18,85.67 trigonal Zn(II)-N3 1.967,1.965

UZELIV[58] [L c39 ZnEt] 79.74 trigonal Zn(II)-N2C 1.954
UZELOB[58] [L c39 Zn(Et)(4-Amino-Pyr)] 78.06 0.91 Td:D4h Zn(II)-N3C 2.007
UZELUH[58] [(L c39 )2 Zn] 85.93, 85.55 0.82 Td:D4h Zn(II)-N4 1.975,1.976
SIYNUL[91] [L c58 NiCl] 40.45 0.04 Td:D4h Ni(II)-N3 Cl 1.879
Ac

SIYPAT[91] [L c66 NiCl] 82.59 0.13 Td:D4h Ni(II)-N3 Cl 1.899

XIXVUX[69] [L c60 TiCl2 ] 83.10 0.50 C 4v:D3h Ti(IV)-N2 Cl2O 1.968
XIXWAE[69] [L c62 TiCl2 ] 80.27 0.47 C 4v:D3h Ti(IV)-N2 Cl2O 1.964
XIXWAE[69] [L c63 TiCl2 ] 87.64 0.50 C 4v:D3h Ti(IV)-N2 Cl2O 1.997
CEPYAZ[68] [L c51 NiCl] 83.58 0.05 Td:D4h Ni(II)-N2 PCl 1.920
CEPXUS[68] [L c53 NiCl] 85.72 0.09 Td:D4h Ni(II)-N2 PCl 1.922
UWUPIM[95] [L c72 Cu(dppb)] 76.66 0.99 Td:D4h Cu(II)-N2 P 2 1.988
UWUPOS[95] [L c73 Cu(dppb)] 82.31 0.96 Td:D4h Cu(II)-N2 P 2 1.964
UWUQAF[95] [L c74 Cu(dppb)] 88.48 0.99 Td:D4h Cu(II)-N2 P 2 1.981
EZOFEE[60] [L c44 Cu(MeCN)] 79.68,81.89 trigonal Cu(I)-N3 (6) 1.925,1.951
EZOFII[60] [L c44 CuCl] 82.85 trigonal Cu(II)-N2 Cl (6) 1.858
EZOFOO[60] [L c44 CuS]2 83.55 0.02 Td:D4h Cu(II)-N2 S 2 (6) 1.879
FAMGIK[63] [L c42 NiBr] 2 77.99 0.98 Td:D4h Ni(II)-N2 Br 2 (6) 1.886
FAMGOQ[63] [L c47 NiBr] 2 88.44 0.99 Td:D4h Ni(II)-N2 Br 2 (6) 1.888
FAMGUW[63] [L c45 NiBr] 2 87.55 0.98 Td:D4h Ni(II)-N2 Br 2 (6) 1.886

51

Page 51 of 60
NAXLAA[67] [L c48 Cu(MeCN)] 86.91 trigonal Cu(I)-N3 (6) 1.883
NAXLEE[67] [L c48 CuO2 ] 88.12 0.02 Td:D4h Cu(II)-N2 O2 (6) 1.828
QEJNID[72] [L c44 Ni(PPh3 )] 89.62 trigonal Ni(I)-N2P (6) 1.908
QEJNOJ[72] [L c47 Ni(PPh3 )] 85.90 trigonal Ni(I)-N2P (6) 1.899
SEYMEP[84] [L c42 CuS]2 79.05 0.04 Td:D4h Cu(II)-N2 S 2 (6) 1.893
SEYMOZ[84] [L c48 CuS]2 89.08 0.03 Td:D4h Cu(II)-N2 S 2 (6) 1.889
TIMLIL[41] [L c2Zn(OBn)]2 86.24 0.98 Td:D4h Zn(II)-N2O2 (6) 1.950
LUSRAT[55] [L c37 Co(µ-Cl)2 Li(THF) 2] 84.61 1.00 Td:D4h Co(II)-N2Cl2 (6) 1.915
Fe(III)-N3Cl2

t
GUTTOF[1] [L c10 FeCl2] 64.06 0.83 C 4v:D3h 1.959
(66)

ip
Co(II)-N3Cl2
GUTTUL[1] [HL c10 CoCl2 ] 84.49 0.67 C 4v:D3h 2.334
(66)
c44
LUSPEV[55] [L ZnN(SiMe 3) 2] 76.79 trigonal Zn(II)-N3 (6) 1.932

cr
LUSPIV[55] [L c44 ZnEt] 87.63,85.13 trigonal Zn(II)-N2C (6) 1.944,1.929
LUSQEW[55] [L c37 Zn] 81.87 0.78 Td:D4h Zn(II)-N4 (6) 1.987
LUSQIA[55] [L c37 ZnMe] 84.00 trigonal Zn(II)-N2C (6) 1.927
LUSQOG[55] [L c37 Zn(µ-OH)]2 76.61 1.00 Td:D4h Zn(II)-N2O2 (6) 1.939

us
LUSQUM[55] [L c37 Zn(C 6 F5 )] 86.68 trigonal Zn(II)-N2C (6) 1.899
Cr(III)-N2Cl2 O2
YUTZUJ[73] [L c49 CrCl2(THF) 2] 87.50 octahedral 1.990
(6)
Cr(III)-N2Cl2 O2
[L c50 CrCl2(THF) 2]

an
YUVBAT[73] 81.22 octahedral 1.984
(6)
c36
See ref [54] [L ZnEt] 78.73 trigonal Zn(II)-N2C (6) 1.971
See ref [50] [L c10 NiMe] 62.69 0.04 Td:D4h Ni(II)-N3 C (66) 1.934
See ref [50] [L c10 NiCF3] 62.91 0.12 Td:D4h Ni(II)-N3 C (66) 1.921
See ref [50] [L c10 NiPh] 57.17 0.12 Td:D4h Ni(II)-N3 C (66) 1.938
M
Motif D Twist angle Geometry Donor set M-NBPA
pentagonal Co(II)-N7
BOJTOJ[97] [L d10 Co(Py)2 ] 76.07 2.085
bipyramidal (65556)
d
BAKDUO[101] [L d1 Ni]BF4 47.26 0.00 Td:D4h Ni(II)-N4 (6556) 1.868
BAKFAW[101] [L d1 Cu]BF4 47.61 0.07 Td:D4h Cu(II)-N4 (6556) 1.932
te

BAKFEA[101] [L d1 Zn(Py)]BF4 53.74 0.55 C 4v:D3h Zn(II)-N5 (6556) 2.054

Fe(III)-N6
BAKFIE[101] [L d1 Fe(SCN) 2] 50.04 octahedral 1.857
(6556)
UXEMEQ[100] [L d11 Cu 2(OAc) 2] 53.44 0.35 Td:D4h Cu(II)-N3 O (66) 1.934
p

UXEMOA[100] [L d12 Cu 2(OAc) 2] 54.91 0.41 Td:D4h Cu(II)-N3 O (66) 1.923

UXEMUG[100] [L d13 Cu 2(OAc) 2] 55.52 0.38 Td:D4h Cu(II)-N3 O (66) 1.924
ce

Cu(II)-N3 O2
UXENER[100] [L d12 Cu 2(DMF)4 ](BF4 )2 60.99 0.27 C 4v:D3h 1.939
(66)

Motif E Twist angle Geometry Donor set M-NBPA

Ac

CEWZEK[105] [L e6Zn 2Et 2] 76.40,81.03 trigonal Zn(II)-N2C (6) 1.931,1.942

CEWZIO[105] [L e5Zn 2Et 2] 84.19 trigonal Zn(II)-N2C (6) 1.928
FIWCEU[109] [L e21 Zn 2 (SO2 Me) 2] 80.80,89.53 0.98,0.98 Td:D4h Zn(II)-N2O2 (6) 1.938
FIWCIY[109] [L e23 Zn 2 (SO2 Me) 2] 82.48,88.43 0.94,0.98 Td:D4h Zn(II)-N2O2 (6) 1.928,1.939
IFETIX[40] [L e4Zn 2Et 2] 73.26,88.50 trigonal Zn(II)-N2C (6) 1.926,1.936
JENJAO[2] [H2L e1 Cu]PF6 58.26, 56.58 linear Cu(I)-N3 (6) 2.640
NEKTUT[110] [L e24 Zn 2 (SO2 Me) 2] 82.08 0.98 Td:D4h Zn(II)-N2O2 (6) 1.959
UGOHEE[108] [L e4ZnEtAlMe 2 ] 89.89 (Zn), 85.38 (Al) trigonal Zn(II)-N2C (6) 1.907
YUBDAB[103] [L e2Fe(THF)] 76.77,80.43 0.97 Td:D4h Fe(II)-N3 O (66) 1.928,1.932
1.883,1.899,1.888,
YUBDEF[103] [L e2FeI] 77.43,80.42,85.66,88.51 0.91,0.93 Td:D4h Fe(III)-N3I (66)
1.902
e2
YUBDIJ[103] [(L Fe)2 O] 74.86,78.02,80.60,86.49 0.94,0.95 Td:D4h Fe(III)-N3O (66) 1.917,1.923,1.926
BEJRIT[104] [L e2Ti(NMe 2 ) 2] 68.65,76.36 0.48 C 4v:D3h Ti(IV)-N5 2.007
BEJQUE[104] [L e2TiCl2] 79.41,80.08 0.30 C 4v:D3h Ti(IV)-N3 Cl2 1.891,1.926
BEJRAL[104] [L e2Ti(THF)Cl2] 64.21,68.84 octahedral Ti(IV)- N3 Cl2 O 2.152,2.113

52

Page 52 of 60
Motif F Cz... Donor Atom Geometry Donor set M-NCz
AHOHEL[115] [L f122 Mn] N/A “linear” Mn(II)-N2 2.042
AHOHIP[115] [L f122 Fe] N/A “linear” Fe(II)-N2 1.974
Fe(III)-N3Cl2
IJAMOV[114] [L f5 FeCl2 ] 0.001,0.082 0.91 C 4v:D3h 1.959
(66)
ROGWAM[113] [L f2 2Zn] 0.127,0.207,0.098,0.203 octahedral Zn(II)-N6 (66) 2.053
f7 Co(II)-N3Cl
TADYIH[70] [L CoCl] 0.120,0.366 0.68 Td:D4h 1.912
(66)
Fe(III)-N3Cl2

t
EDEBOG[49] [L f2 FeCl2 ] 0.339,0.085 0.90 C 4v:D3h 1.967
(66)

ip
XOBPUB[120] [L f13Cu] 0.283 distorted trigonal Cu(I)-NC 2 2.017
XIZLEZ[120] [L f13CuCl] 0.00 0.65 Td:D4h Cu(II)-NC 2Cl 1.956
XIZLID[120] [L f13NiOH] N/A square planar Ni(II)-NC 2 H 1.902

cr
Motif G Cz...N2/4 Geometry Donor set M-NCz
QUQYAC[126] [L g1Ni] 0.401,0.651 0.01 Td:D4h Ni(II)-N4 (6666) 1.851
Zn(II)-N4

us
ref [129] [L g1Zn] 0.137,0.529 0.03 Td:D4h 1.954
(6666)
Co(II)-N4O2
EJICAC[132] [L g8Co(OH2)(THF)] 0.642,0.650,0.593,0.613 octahedral 1.950,1.934
(6666)

an
Motif H M...N4 plane Geometry Donor set M-NCz
1.904,1.905,1.908,
ref [140] [L h7 Ni] 0.019,0.029 0.03 Td:D4h Ni(II)-N4 (6666) 1.919,1.924,1.925,
1.929,1.930
Twist angle: the angle between the mean planes of the two phenyl rings making up the diphenylamine unit. Tetrahedral
M
distortion parameter [ω/90]: 0 = square planar (D4h); 1 = tetrahedral (Td); where ω is the dihedral angle between the chelate
ring planes N—Cu—N and N—Cu—O[147]. Trigonality distortion parameter τ = [(β − α)/60]: 0 = square pyramidal (C4v);
1 = trigonal bipyramidal (D3h); where β is the largest of the basal angles and α is the second largest[148].
d
Table 7: Distribution of metal ions, and number of complexes, across the 10 motifs identified (Figure 2) for the 385
complexes reviewed herein.
Motifs
te

A B C D E F G H I J sum
Sc +3 36 36
p

Ti +4 7 3 10
V 1 1
ce

Cr 13 2 15
Mn +2 1 1 2
Fe +2 1 1 6 1 3 12
Ac

Fe +3 1 1 3 1 2 1 9
Metals

Co +2 1 2 7 10 3 3 10 36
Co +3 1 1 2
Ni +2 5 2 28 9 9 6 1 3 63
Ni +1 2 2
Cu +2 25 2 14 15 6 1 3 2 68
Cu +1 9 1 10
Zn +2 9 2 47 2 47 2 5 114
Mix metals 3 1 1 5
Totals 47 10 172 38 55 28 9 7 3 16 385

53

Page 53 of 60
Table 8: Distribution of the number of complexes, and of the three most common metal ions (Zn, Cu and Ni), across the 10
motifs (Figure 2), for the 96 complexes in the CSD.

CSD CSD
Motif CSD(total) CSD (Ni) CSD(other)
(Zn) (Cu)
A 1 0 0 1 0
B 8 1 2 2 3

t
C 51 16 10 16 9

ip
D 9 1 5 1 2
E 14 7 1 0 6
F 9 1 2 1 5

cr
G 3 1 0 1 1
H 1 0 0 1 0

us
I 0 0 0 0 0
J 0 0 0 0 0
total 96 27 20 23 26

an
The M—N bond lengths generally lie between 1.85
and 2.0 Å. The triarylamine complexes (Motif B)
have consistently higher M—NTPA bond lengths
M
(2.24 ± 0.19 Å), which is due to weaker
coordination, since the central amine is uncharged
and has increased π character due to the
neighbouring phenyl rings, and the metal centres are
d
number structurally characterised almost doubled
over the same period (from 55 to 96). The latter
statistic is particularly telling, indicating
considerable growth in interest in these systems,
something which we predict will continue to grow
sharply over the next few years.

satisfied by the three coordinated negatively charged Ten motifs (A-J, Figures 2, 47 and 48) have been
carboxylate groups. The diphenylamine- and identified amongst the ligands that generated these
te

carbazole-based complexes have shorter M—NDPA 385 complexes. Possibly due to the relative ease of
and M—NCz distances (1.96 ± 0.13 Å and 1.95 ± ligand synthesis, in combination with considerable
0.10 Å respectively), since in all but two cases the interest in the resulting complexes as catalysts, most
p

central amine is deprotonated and binds quite of the growth between 2011 and 2014 occurred in
strongly. The two exceptions are the copper(I) motif C, the acyclic iminomethyl or oxazole
ce

complex, [H2La1CuI]PF6, and the cobalt(II) complex,
[HLc3CoIICl2], both of which feature a neutral
diphenylamine-based ligand. In these two structures
the hydrogen atom on the central amine remains,
Ac
substituted diarylamines – nearly half of the
complexes in this review fall into this category, and
the number structurally characterised Motif C
complexes (Table 7) almost doubled over the three

meaning the ligands are neutral and not anionic,
resulting in longer M— NDPA bond lengths of 2.640
and 2.334 Å respectively. The ligands within this
review are many and varied, as seen by the range of
coordination geometries seen in the structurally
characterised complexes and which are shown to
depend strongly on the ligand substitution and
choice of co-ligand.
4. Concluding Remarks
years to 2014.
In contrast to the dramatic growth of examples of
Motif C complexes over the last 3 years, there has
been no expansion of the range of complexes of
porphyrin-like carbazole macrocycles in Motifs G
and H, and no new structures reported. This may be
due in part the synthetic complexity of accessing
such ligands, combined with limited solubility of the
resulting complexes.

The number of complexes matching the SciFinder® In most of the 385 complexes, the ligand is
Scholar sub-structure search fragment (Figure 1) deprotonated at the diphenylamine NH. From the
increased by about 25% over the three years from available experimental data, complexes within Motif
January 2011 to April 2014 (from 230 to 408). The

54

Page 54 of 60
A used NaOH or KOH as the base for
deprotonation. Motifs B and D mostly used
trimethylamine as their base, but for Motif D,
pyridine or M(OAc)2 salts were also employed.
Motif C used almost exclusively nBuLi, with a few
examples of the use of Zn[N(SiMe3)2]2 or ZnEt2.
ZnEt2 was also used for Motif E complexes, along
with KBn and Na/KOtBu. Complexes of Motif F
Another key field of interest evident in this review is
that of metalloenzyme modelling, primarily copper
complexes, mainly of Motifs A and C, were
prepared. Several other research interests and
applications were also reported, including
photophysical studies, and the use of such
complexes for medical (drugs, PDT/MRI contrast
agents) or agrichemical purposes. Over the last few

t
used either NaH or nBuLi. years, growth in the number of complexes of Motifs

ip
A-J for application in these fields has been modest,
The majority of these complexes were prepared for when compared to the significant growth seen for
use as catalysts, many showing excellent catalytic applications in the catalyst field.

cr
activity for the polymerisation of various olefins.
These catalysts primarily featured zinc or nickel In summary, this selection of complexes has a wide
ions. Not surprisingly many have thus been range of applications from medicinal purposes to

patented. Several of the complexes within this
review were also tested for their ability to catalyse
various other transformations, with varying success,
including the asymmetric catalysis of reactions such
us
photoluminescence. Motif A features mainly
complexes useful as medicines. Motif C, E and F
complexes are focused on various catalytic
processes e.g. norbornene polymerisation, ring

as Nozaki–Hiyama allylation, Henry, Friedel–
Crafts, ketone hydro-silylation, cyclopropanation
and nitroalkane Michael addition reactions. Over
time many of the more successful catalysts have
M
been revisited with new synthetic techniques
allowing access to subtle modifications of the core
structure yielding improved results in some
instances. In more recent years the rapid increase in
d
access to, and importance of, crystallography[149]
has meant that a much larger proportion of the
te
an
opening polymerisation of cyclic esters. Motif G, H
and I complexes have photophysical applications.
These examples of complexes featuring the
coordinated di-o-tolyamine moiety of interest
(Figure 1) clearly show a wide range of interesting
properties and potential applications, and have a
bright future. Indeed this research group is actively
pursuing a number of new Motif A-I systems[98-
101][150, 151], with these applications in mind.

complexes synthesised are being analysed Acknowledgements

structurally. In the area of catalysis this is proving We thank the Department of Chemistry and
particularly influential as being able to observe in University of Otago for support, including PhD
p

the solid state how altering the outer or auxiliary scholarships to SJM and SAC.
groups affects the active site facilitates the planning
ce

of further fine tuning of the ligand scaffold. List of abbreviations

The nature of the donors present in these ligands has AAS atomic absorption spectroscopy
expanded from being heavily nitrogen based to the AcOH acetic acid
Ac

inclusion of both oxygen and nitrogen donors and AD actinomycin D

then to a few ligands that also contain phosphorus or AnIm anilido-imine
sulfur donor atoms. This shift to include a wider β-BL β-butyrolactone
range of donor atoms clearly dramatically effects the BINAP 2,2’-bis(diphenyl-phosphino)-
properties of the metal ions and the uses of the 1,1’-binaphthyl
resulting complexes, facilitating access into new Bn benzyl
areas of catalysis and other applications. Clearly, BnOH benyl alcohol
ligands based on this search fragment show great nBuLi n-butyllithium
promise for a variety of potential applications tBuLi t-butyllithium
particularly in the area of catalysis using asymmetric CB chlorobenzene
or acyclic pincer style ligands, and there is plenty of CHD cyclohexadiene
room for further development. CHO cyclohexane oxide
ɛ-CL ɛ-caprolactone
COD cyclooctadiene

55

Page 55 of 60
COT cyclooctatetraene Phen 1,10-phenanthroline
CV cyclic voltammogram PNBE polynorbornene
DABCO 1,4-diazabicyclo[2.2.2]octane ROMP ring opening metathesis
dba dibenzylideneacetone polymerisation
DCM dichloromethane ROP ring-opening polymerisation
DDQ 2,3-dichloro-5,6-dicyano-1,4- RT room temperature
benzoquinone SMM single molecule magnet
DFT density functional theory TBAF tetra-n-butylammonium fluoride

t
dipy 2,2’-dipyridyl TCB trichlorobenzene

ip
DMAP 4-dimethaminopyridine TEA triethylamine
DMF dimethylformamide Terpy 2,2’,2”-terpyridyl
DMSO dimethylsulfoxide TFA trifluoroacetic acid

cr
DPA diphenylamine THF tetrahydrofuran
DPEPhos bis(2-diphenyl- TM transition metal
phosphinophenyl)ether TMEDA tetramethylethylenediamine

us
DPPF 1,1′-bis(diphenyl- TPA triphenylamine
phosphino)ferrocene UV-vis ultraviolet-visible
ESI electronic supplementary XPS X-ray photoelectron spectroscopy
information

an
ESR electron spin resonance
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