Inorganica Chimica Acta 362 (2009) 48094812

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Inorganica Chimica Acta

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Zinc complexes of a tripodal ligand containing three different N-heterocyclic donor functions
Marit Wagner, Christian Limberg *
Institut fr Anorganische Chemie, Humboldt-Universitt zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany

a r t i c l e

i n f o

a b s t r a c t
The coordination chemistry of a chiral tripodal ligand L containing pyridyl, imidazolyl and pyrazolyl donor functions has been investigated in combination with zinc(II). While the reaction of a racemic mixture of L with ZnX2 (X = Cl, Br) leads to complexes LZnX2 with tetrahedrally coordinated zinc centres (the pyridyl donor function remains pending), the employment of Zn(ClO4)2 leads to the sandwich complex [L2Zn](ClO4)2 which due to the two possible congurations for L (S and R) occurs in form of two diastereomers (the meso form and the enantiomeric pair SS/RR). The crystal structures of all three compounds are discussed. 2009 Elsevier B.V. All rights reserved.

Article history: Received 17 March 2009 Accepted 8 July 2009 Available online 14 July 2009 Keywords: Coordination chemistry Zinc N-ligands Chirality Complexes

1. Introduction Histidine moieties are often found as ligands within the prosthetic groups of metalloenzymes [13], and in proteins like tyrosinase [1], carboanhydrase [2] or hemeerythrine [3] even three histidine-based imidazole residues are coordinated to a metal centre. Consequently, a lot of research has been dedicated to the design of multipodal ligands with N-heterocyclic donor functions for an employment in biomimetic chemistry. A prominent example is the tris(pyrazolyl)borate ligand (Tp) [4], which makes use of three pyrazole donors, while three imidazole units are found in tris(imidazolyl)methanes [5]. Pyridyl residues are often used to mimic histidines, too, and hence for instance the tetrapodal TPA (tris(pyridylmethyl)amine), where three pyridyl donors are linked to an amine, has been used a lot [6]. The reaction pockets of metalloenzymes are intrinsically chiral, and in some cases (e.g. in the active centres of cytochromes P450 [7,8] or the lipoxygenases [9]) they are responsible for the stereoselectivity observed for the corresponding enzyme reactions. We have therefore recently developed a novel chiral tripodal ligand (L in Scheme 1) that contains three different donor functions approved in biomimetic or bioinspired chemistry, namely one imidazolyl, one pyrazolyl and one pyridyl residue, and reported rst results concerning its iron chemistry [10]. Since carboanhydrase (vide supra) is a zinc enzyme, naturally we were also interested in the zinc chemistry of L [11].

* Corresponding author. Tel.: +49 030 2093 7382; fax: +49 30 2093 6966. E-mail address: christian.limberg@chemie.hu-berlin.de (C. Limberg). 0020-1693/$ - see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.ica.2009.07.007

In the carboanhydrase (CA) three histidine moieties are coordinating a Zn2+ ion, which reaches a distorted tetrahedral coordination sphere by the additional binding of a water molecule [11]. Through coordination at the zinc centre the aqua ligand gets acidied, and a proton loss leads to a nucleophilic ZnOH group that readily attacks CO2 converting it to HOCO2. Hence the enzyme plays an essential physiological role in respiration and CO2/HCO3 equilibration [2]. Numerous studies have been reported that deal with the simulation of this reaction with the aid of molecular model compounds in order to reproduce single steps of the CA mechanism [11]. Many models published to date use tripodal ligands with three nitrogen donors, and particular attention has been paid to Tp ligands with bulky substituents in the 3-positions [12]. This way the formation of Tp2Zn instead of TpZnX complexes is excluded, and a reaction pocket is generated that helps to perform selective conversions. While Tp is an anionic ligand also neutral N,N,N ligands have been employed in CA modelling studies, such as tris(imidazolyl)carbinole [13], tris(imidazolyl)alkane [14] and tris(imidazolyl)phosphine [15]. However, structurally characterised tetrahedral complexes thereof are rather rare, and unfortunately this is especially the case for hydroxo or aqua complexes, which would be the most interesting species [11]. In contrast, tris(benzimidazolylmethyl)amine ligands (which provide an additional N donor function) allow a model chemistry which is almost as versatile as the one that utilises Tp complexes [16]. On the other hand tris(pyrid-2-yl)phosphine [17] and also tris(pyrazol-1yl)methane [18] tend to form bisligand complexes. With 1,4,7-trimethyl-1,4,7-triazacyclononane a dinuclear complex with a bridging hydroxide ligand has been isolated [19]. The aim of the

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M. Wagner, C. Limberg / Inorganica Chimica Acta 362 (2009) 48094812

O N N Br N N N Zn 2 Br
t

O Bu N ZnBr2 N N N N
t

O Bu N ZnCl2 N Cl N N N Zn 1 Cl
t

Bu

L
Scheme 1. Syntheses of the zinc(II) complexes 1 and 2.

investigation which is reported here was the exploitation of the potential of our novel ligand L in this context. 2. Experimental Apart from the ligand synthesis all manipulations were carried out in a glove-box, where the anhydrous ZnX2 salts (X = Cl, Br) were stored. Apart from that the syntheses of the compounds in principal do not require inert atmospheres. In fact the preparation of 3 was performed under normal air. The 1H and 13C NMR spectra were recorded on a Bruker AV 400 NMR spectrometer (1H 400.13 MHz; 13C 100.63 MHz) with CDCl3 or CD3CN as solvent at 20 C. The 1H and 13C NMR spectra were calibrated against the residual proton and natural abundance 13C resonances of the deuterated solvent (CDCl3 dH 7.26 ppm, dC 77.00 ppm, CD3CN dH 1.94 ppm, dC 1.24 ppm). Microanalyses were performed on a Leco CHNS-932 elemental analyser or on a HEKAtech EURO EA. ESIMS-spectra were recorded on an Agilent Technologies 6210 Time-of-Flight LC/MS. Infrared (IR) spectra were recorded using samples prepared as KBr pellets with a Digilab Excalibur FTS 4000 FTIR-spectrometer. Solvents were dried using a Braun Solvent Purication System. L was synthesized as described earlier [10]. 2.1. Synthesis of [LZnCl2] (1) About 100 mg (0.295 mmol, 1 eq.) of L were added to a solution of 40 mg (0.295 mmol) of ZnCl2 in 10 mL acetonitrile. After stirring of the reaction mixture overnight the solvent was removed and the solid was washed with 5 mL of thf. After drying, pure 1 was obtained in form of a white solid (105 mg, 0.22 mmol, 75%). Crystals suitable for single crystal X-ray diffraction studies can be obtained by evaporating the solvent from a saturated diethylether solution. 1 H NMR (400 MHz, CDCl3): d = 1.32 (s, 9 H, C(CH3)3), 3.18 (s, 3H, OCH3), 3.41 (s, 3H, Im NCH3), 4.32 (s, 3H, Pz NCH3), 6.12 (s, 1H, Pz CH-4), 7.03 (d, 3JH,H = 1.413 Hz, 1H, Im CH-5), 7.25 (m, 1H, Py CH), 7.31 (d, 3JH,H = 1.453 Hz, 1H, Im CH-4), 7.54 (m, 1H, Py CH), 7.73 (m 1H, Py CH), 8.59 (m, 1H, Py CH); 13C NMR (CDCl3) = 29.3 (C(CH3)3), 31.5 (C(CH3)3), 35.0 (Im NCH3), 39.9 (Pz NCH3), 53.4 (OCH3), 80.1 (CqOCH3), 104.6 (Pz CH-4), 120.9 (Py CH), 123.4 (Py CH), 124.6 (Im CH-5), 125.9 (Im CH-4), 137.8 (Py CH), 144.6 (Im Cq-2), 149.5 (Py CH), 155.1 (Pz Cq-5); IR (KBr): 3151 (w), 3122 (w), 2960 (s), 2937 (m), 2921 (m), 2877 (m), 2830 (w), 1658 (w), 1587 (m), 1536 (m), 1500 (m), 1466 (m), 1432 (m), 1378 (m), 1370 (m), 1285 (m), 1261 (m), 1246 (m), 2117 (w), 1204 (w), 1156 (m), 1104 (s), 1076 (s), 1045 (m), 1021 (w), 982 (m), 909 (m), 901 (m), 811 (s), 784 (s), 766 (m), 757 (m), 713 (m), 659 (m), 619 (m) cm1, ESI-MS (pos, MeCN): m/z = 438.113 (calcd. for [LZnCl]+ 438.104); elemental Anal. Calc. for C19H25Cl2N5OZn (473.07 g/mol): C, 47.97; H, 5.30; N, 14.90; Cl, 14.90. Found: C, 47.99; H, 5.40; N, 14.88; Cl, 14.63%. 2.2. Synthesis of [LZnBr2] (2) About 500 mg (1.47 mmol, 1 eq.) of L were added to a solution of 332 mg (1.47 mmol) of ZnBr2 in 30 mL thf. After stirring of the

reaction mixture overnight the resulting solution was concentrated to 15 mL, which led to a white precipitate of LZnBr2, 2. After ltering the solid was washed with 5 mL of thf and after drying 2 was obtained in form of a white solid (516 mg, 0.91 mmol, 62%). Crystals suitable for single crystal X-ray diffraction studies can be obtained by evaporating the solvent from a saturated acetonitrile solution. According to the results of the XRD these crystals contain one molecule of acetonitrile per two molecules of 2. 1H NMR (400 MHz, CDCl3): d = 1.32 (s, 9 H, C(CH3)3), 3.18 (s, 3H, OCH3), 3.39 (s, 3H, Im NCH3), 4.35 (s, 3H, Pz NCH3), 6.09 (s, 1H, Pz CH4), 7.04 (d, 3JH,H = 1.37 Hz, 1H, Im CH-5), 7.23 (m, 1H, Py CH), 7.30 (d, 3JH,H = 1.50 Hz, 1H, Im CH-4), 7.55 (m, 1H, Py CH), 7.72 (m, 1H, Py CH), 8.55 (m, 1H, Py CH); 13C NMR (CDCl3) = 29.3 (C(CH3)3), 31.5 (C(CH3)3), 34.9 (Im NCH3), 40.2 (Pz NCH3), 53.6 (OCH3), 80.2 (CqOCH3), 104.7 (Pz CH-4), 120.8 (Py CH), 123.4 (Py CH), 124.4 (Im CH-5), 125.9 (Im CH-4), 137.5 (Py CH), 144.5 (Im Cq-2), 149.6 (Py CH), 155.2 (Pz Cq-5); IR (KBr): 3120 (m), 2972 (s), 2940 (m), 2933(m), 2868 (m), 2845 (w), 1733 (w), 1586 (m), 1533 (m), 1500 (m), 1463 (m), 1430 (m), 1378 (m), 1370 (m), 1286 (m), 1244 (m), 1162 (m), 1103 (s), 1073 (s), 1045 (m), 982 (m), 907 (m), 807 (m), 782 (s), 754 (m), 712 (m), 704 (m), 658 (w), 619 (w) cm1, ESI-MS (pos, MeCN): m/z = 484.044 (calcd. for [LZnBr]+ 484.053); elemental Anal. Calc. for 20.5 MeCN C20H26.5Br2N5.5OZn (585.16 g/mol): C, 41.05; H, 4.56; N, 13.17; Br, 27.31. Found: C, 41.00; H, 4.55; N, 13.02; Br, 27.29%. 2.3. Synthesis of [L2Zn] (ClO4)2 (3) Caution: Perchlorate salts are potentially explosive and should be handled with care. 200 mg (0.59 mmol, 1 eq.) of L were added to a solution of 219 mg (0.295 mmol) of Zn(ClO4)26H2O in 10 mL thf. After stirring of the reaction mixture overnight a white precipitate of 3 had formed. After ltering the solid was washed with 5 mL of thf, and after drying pure 3 was obtained in form of a white solid (300 mg, 0.31 mmol, 54%). Crystals suitable for single crystal Xray diffraction studies can be obtained by slow diffusion of thf into a saturated acetonitrile solution. 1H NMR (400 MHz, CD3CN): d = 1.32 (s, 9 H, C(CH3)3), 1.36 (s, 9 H, C(CH3)3), 3.35 (s, br, 3 H, NCH3), 3.65 (s, br, 3 H, NCH3), 3.79 (s, 3 H, OCH3), 3.82 (s, 3 H, OCH3), 3.89 (s, 3 H, NCH3), 3.91 (s, 3 H, NCH3), 6.37 (d, 1 H, J = 1.6 Hz, Im or Py CH), 6.51 (s, 1 H, Pz CH-4), 6.52 (s, 1 H, Pz CH-4), 6.67 (s, br, 1 H, Im or Py CH), 7.07 (d, 1 H, J = 1.5 Hz, Im or Py CH), 7.14 (d, 1 H, J = 1.2 Hz, Im or Py CH), 7.18 (m, 2 H, Im and/or Py CH), 7.42 (s, br, 2H, Im or Py CH), 8.03 (m, 2 H, Py CH), 8.10 (m, 2 H, Py CH; 13C NMR (CD3CN) = 29.21 C(CH3)3), 29.23 C(CH3)3), 32.31 (C(CH3)3), 32.33 (C(CH3)3), 36.13 (NCH3), 36.20 (NCH3), 39.46 (NCH3), 39.77 (NCH3), 56.16 (OCH3), 56.30 (OCH3), 82.19 (CqOCH3), 82.27 (CqOCH3), 105.18 (Pz CH-4), 105.32 (Pz CH-4), 120.16 (Im or Py CH), 120.26 (Im or Py CH), 124.72 (Im or Py CH), 124.92 (Im or Py CH), 126.45 (Im or Py CH), 126.63 (Im or Py CH), 126.68 (Im or Py CH), 126.76 (Im or Py CH), 141.40 (Py CH), 141.56 (Py CH), 147.06 (Cq), 147.15 (Cq), 149.52 (Cq), 149.74 (Cq), 152.04 (Cq), 152.22 (Cq), 156.76 (Cq), 156.92 (Cq), 158.07 (Cq), 158.20 (Cq).); IR (KBr): 3152 (m), 3126 (m), 2985 (m), 2974 (m), 2967 (m), 2961 (m), 2947 (m), 2941 (m), 2930

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(m), 2905 (m), 2877 (m), 2838 (m), 2013 (m), 1600 (m), 1572 (w), 1541 (w), 1519 (m), 1489 (m), 1466 (m), 1441 (m), 1417 (w), 1369 (m), 1284 (w), 1244 (m), 1202 (m), 1151 (w), 1127 (s), 1106 (s), 1083 (s), 1037(m), 985 (m), 957 (m), 907 (m), 888 (m), 842 (m), 780 (s), 714 (m), 623 (m), 521 (m) cm1; elemental Anal. Calc. for C38H50Cl2N10O10Zn (943.16 g/mol): C, 48.39; H, 5.34; N, 14.85; Cl, 7.52. Found: C, 48.11; H, 5.23; N, 14.28; Cl, 7.75%.

3. Results and discussion While zinc(II) preferably binds four ligands in a (often distorted) tetrahedral geometry, cases with 5- or even 6-coordinated zinc ions are known, too: in the absence of ligand eld stabilisations, which cannot occur for a d10 metal centre, this is simply an issue of the size of the ligands, their electronic properties (which determine the Lewis acidity of the metal centre) and the utilisation of chelating effects [11]. Hence, rst of all the behaviour of L in contact with ZnCl2 and ZnBr2 was tested. As this investigation does not focus on the chirality, a racemic mixture has been employed in all studies. Addition of L to solutions of theses salts in acetonitrile and thf, respectively, led to colourless solutions from which the products could be isolated as white powders via adequate work-up. Characterisation by NMR and IR spectroscopy, elemental analysis and ESI/MS revealed them as LZnX2 (X = Cl, 1, and Br, 2). Crystals of these compounds could be obtained by evaporation of the solvents from saturated solutions. They contained both enantiomers within the unit cell, and only the molecular structure

Fig. 1. Molecular structure of [LZnCl2], 1. Hydrogen atoms are omitted for clarity. Selected bond lengths [] and angles []: Cl1Zn 2.2487(17), Cl2Zn 2.2580(15), N1Zn 2.061(4), N3Zn 2.070(4); N1ZnN3 85.98(15), N1ZnCl1 107.76(12), N3 ZnCl1 115.99(13), N1ZnCl2 117.61(18), N3ZnCl2 110.59(13), Cl1ZnCl2 115.6(6).

of 1 with L in the S conguration is shown in Fig. 1 (the one of 2 is very similar and shown in Fig. S1 of the Supplementary material). Despite its three donor functions the ligand coordinates in a bidentate fashion via the imidazolyl and the pyrazolyl donors, while the pyridyl unit remains pending. A similar behaviour of L had been observed before in the complexation reaction of FeCl2 [10], and the fact that the pyridyl unit was left dangling (instead of the less basic pyrazole function) had been rationalised by arguments based on the sterics: Assuming that the strongest donor imidazole coordinates rst, apparently a chelate with an additional r-donor reaches a more favourable orbital interaction (aligned with the MN vectors), if this donor is incorporated into the 5membered ring of pyrazole instead of the 6-membered pyridyl ring. The angles at the zinc centre of 1 vary between 85.98(15) (N1ZnN3) and 117.61(18) (N1ZnCl2), indicating a signicant distortion of the tetrahedral coordination sphere. The 6-membered chelate-ring is almost planar. According to the NMR data the pyridyl donor neither coordinates in solution. Comparing the resonance positions of the methine protons belonging to the pyridyl units of the free ligand L and 1 a maximum shift of 0.13 ppm was observed for CDCl3 solutions (0.13, 0.12, 0.03, 0.06 ppm). To get an idea what kind of shift one would have to expect on pyridyl coordination, the precursor for L, (1-methylimidazole-2-yl)(pyridine-2-yl)methanone was dissolved in CD3CN and the inuence of the addition of 1 eq. ZnCl2 on the pyridyl signals in the 1H NMR spectrum was determined. A much more pronounced maximum shift of 0.56 ppm (0.56, 0.45, 0.46, 0.16 ppm) was observed, which argues against the coordination of the pyridyl arm in solutions of 1. Complexes 1 and 2 as such can of course not appropriately model the (His)3Zn moiety of CA, and therefore attempts were made to remove one or both halide ligands from the coordination sphere of the zinc centre by reaction with AgOTf and AgClO4, to allow for the coordination of the pyridyl function and eventually an aqua ligand. However, 1H NMR spectra recorded after such experiments indicated the formation of product mixtures, as several sets of signals for L were observed. One of these sets contained broad and doubled signals, characteristic of L2Zn2+ (compare below). Hence, no clean reaction occurs, and it was not possible to isolate a pure product from such conversions. Finally, a zinc starting material was employed that contained weakly coordinating anions already, namely Zn(ClO4)26H2O, whose employment in Tp chemistry had allowed for the straight forward synthesis of TpZnOH [12b]. An equimolar reaction led to the precipitation of a white solid that was characterized rst by means of NMR and IR spectroscopy. A double set of signals for L in the NMR spectra already indicated the presence of two ligands per Zn centre, since one set should be expected then for a combination of the ligands in two different congurations (the meso form) and another one for the diastereomeric combination S/S as well as its enantiomer R/R. Elemental analysis conrmed the

2+

O O 2 N N N N N
t

N Zn(ClO4)2(H2O)6
t

Bu

N N N Zn N N O

Bu 2 ClO4-

Bu

N N N

3
Scheme 2. Synthesis of zinc(II) complex 3.

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sents a strongly coordinating ligand such as a halide. Attempts to replace the halide ligands by weakly coordinating anions led to homoleptic 1:2 complexes [ZnL2]2+. Bearing in mind a potential modelling of the CA reactivity, bulky groups should thus be introduced at least at some of the N-heterocyclic donors in order to favour the formation of 1:1 complexes [LZn]2+. The synthesis of corresponding sterically hindered derivatives of L will be the subject of future research. Acknowledgments We are grateful to the Fonds der Chemischen Industrie, the Bundesministerium fr Bildung, Wissenschaft, Forschung und Technologie and the Dr. Otto Rhm Gedchtnisstiftung for nancial support as well as to Bayer Services GmbH & Co. OHG, BASF AG and Sasol GmbH for the supply of chemicals. We also would like to thank C. Knispel, P. Neubauer and B. Ziemer for crystal structure analyses and C. Jankowski for the preparation of starting materials. Appendix A. Supplementary material CCDC 716535, 716536 and 716537 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.ica.2009.07.007. References
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Fig. 2. Molecular structure of the cation [L2Zn]2+ of 3. Hydrogen atoms are omitted for clarity. Selected bond lengths [] and angles []: N1Zn 2.222(5), N4Zn 2.051(5), N5Zn 2.210(5); N4ZnN50 87.62(18), N4ZnN5 92.38(18), N4ZnN1 81.16(18), N40 ZnN1 98.84(18), N50 ZnN1 86.35(17), N5ZnN1 93.65(17), N40 ZnN5 87.62(18).

constitution [L2Zn](ClO4)2, 3, (Scheme 2) and an X-ray diffraction analysis of crystals grown from acetonitrile revealed the structural arrangement of 3 in a crystal containing exclusively the meso (RS) diastereomer. Fig. 2 shows the molecular structure of its cation. The zinc centre is coordinated by the two ligands L in a distorted octahedral fashion, similarly as observed in case of the bis(tris(3,4,5-trimethylpyrazolyl)methane zinc complex [18], the bis(tris(3,5-dimethylpyrazolyl)borato) zinc complex [20] and the corresponding iron(II) complex [L2Fe(OTf)2] [10]. The cation of 3 is centrosymmetric due to the location of the zinc ion on a crystallographic inversion centre, and the angles at the zinc centre of 3 vary between 81.16(18) (N4ZnN1) and 98.84 (N40 ZnN1). The bond between the zinc atom and the imidazole nitrogen atom (ZnN4) is the shortest one (2.051(5) ) of the zinc nitrogen bonds while the distance of the zinc centre to the nitrogen atom of the pyrazolyl residue is the longest one (ZnN1 2.222(5) ). Knowing that the equimolar reaction of L with Zn(ClO4)26H2O selectively leads to 3 with a Zn to L ratio of 1:2 the reaction was repeated with an adjusted stoichiometry, which, naturally, signicantly improved the yield. In order to test, whether selective formation of 3 is due to its precipitation from the solvent (thf) employed, the reaction was repeated in CH3CN where 3 is soluble. However, again the characteristic double set of signals was observed. In addition a further set could be identied (integration ratio 1:0.32) that belongs to a so far unassigned species. According to NMR studies the diastereomers which give rise to the two sets of signals do not interconvert and they are not part of an equilibrium: The integral ratio of the two sets does not vary with temperature (RT ? 30 C) and addition of L to a CD3CN solution does not lead to a line broadening or a signal shift (only to a new set of signals for free L). Treatment of L with two eq. of Zn(ClO4)2 that could be imagined to shift a potential equilibrium into the direction of a LZn2+ species again mainly led to the signals of 3, which apparently represents the thermodynamic hole of the system. 4. Conclusions The results described show that the reaction of the novel ligand L with compounds ZnX2 lead to 4-coordinate zinc complexes LZnX2 (with the pyridyl donor function remaining dangling), if X repre-

[7] [8] [9] [10] [11] [12]

[13] [14] [15]

[16]

[17] [18] [19] [20]