DOI: 10.1002/zaac.

200500369

Unusual Coordination Modes of Tris(pyrazol-1-yl)borates: Synthesis and Solid State Structures of Sodium[(dimethylamino)tris(pyrazol-1-yl)borate], Potassium[(dimethylamino)tris(pyrazol-1-yl)borate], and Potassium[phenyltris(pyrazol-1-yl)borate]
Susanne Bieller, Michael Bolte, Hans-Wolfram Lerner, and Matthias Wagner*
Frankfurt am Main, Institut fr Anorganische Chemie der J. W. Goethe-Universitt Received September 15th, 2005. Abstract. We report the optimized syntheses and the solid state structures of the alkali metal tris(pyrazol-1-yl)borates M[Me2NBpz3] (M Na (1), K (2); pz pyrazol-1-yl) and K[PhBpz3] (3). Even though 1 and 2 consist of polymeric chains in the solid state, it is possible to identify subunits where the [Me2NBpz3] ion acts as tridentate ligand towards Na and K and binds via two of its pyrazolyl rings and its dimethylamino nitrogen atom (3Npz,Npz,NNMe). In 3, the ligand [PhBpz3] employs two pyrazolyl donors and the -face of its phenyl substituent for potassium coordination (3N,N,C).

Keywords: Sodium; Potassium; Tris(pyrazol-1-yl)borates; Scorpionate ligand; Crystal Structure; NMR Spectroscopy

1 Introduction
Since the first synthesis of tris(pyrazol-1-yl)borate [HBpz3] (pz pyrazol-1-yl) by Trofimenko in 1966 [1], many efforts have been made to introduce substituents into the pyrazolyl rings. In this context, tris(pyrazol-1-yl)borates (scorpionates) bearing bulky groups at the 3-positions of their pyrazolyl rings turned out to be particularly useful with regard to the kinetic stabilization of highly reactive metal complex fragments. Scorpionates with substituents other than hydrogen at boron, however, are far less investigated, and the vast majority of tris(pyrazol-1-yl)borates [RBpz3] still bears either a hydrogen atom or a phenyl ring as fourth substituent R. We are interested in the further development of [RBpz3] type ligands mainly for three reasons: (1) The steric demand as well as the electronic properties of R can be expected to influence the coordination behaviour of the tris(pyrazol-1-yl)borate donor. Evidence for this assumption comes, for example, from an investigation of the ferrocenyl scorpionates [FcBpz3] and [1,1-fc(Bpz3)2]2 (Fc (C5H5)Fe(C5H4); fc (C5H4)2Fe) [2]. (2) The substituent R may be used to link two scorpionate fragments together in order to generate ditopic ligand systems like [1,1fc(Bpz3)2]2 or the p-phenylene bridged species [pC6H4(Bpz3)2]2 that was recently developed by our group [3]. (3) Tris(pyrazol-1-yl)borates are usually regarded as tridentate ligands establishing a 3Npz,Npz,Npz coordination

* Prof. Dr. M. Wagner Institut fr Anorganische Chemie der J. W. Goethe-Universitt Marie-Curie-Str. 11 D-60439 Frankfurt (Main) Fax: 49(0)69-79829260 E-mail: Matthias.Wagner@chemie.uni-frankfurt.de
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mode. The question thus arises, whether this is necessarily true also for those derivatives [RBpz3] where R possesses Lewis-basic properties (e.g. R NR2, OR) or may act as -donor (e.g. R Ph) towards a metal centre. In 1981, Niedenzu reported on the reaction of (dimethylamino)boranes with pyrazole in varying stoichiometric ratios for the formation of amino(pyrazol-1-yl)boranes [4]. In the course of these investigations, he synthesized the ligand [Me2NBpz3], which was subsequently employed in the preparation of the molybdenum complex [Me2NBpz3]Mo(CO)2(3-allyl) [5]. NMR spectroscopy on this compound suggested a 3Npz,Npz,NNMe binding mode of the scorpionate ligand (cf. A, Figure 1) rather than the common 3Npz,Npz,Npz coordination (cf. B, Figure 1). Until now, this finding could not be proven by a crystal structure analysis. The coordination chemistry of the phenyl substituted ligand [PhBpz3] has been the topic of extensive studies comprising a large number of transition metals [6]. However, only few crystal structure analyses [79] have been carried out according to the current version of the Cambridge Structural Database [10]. In five of these cases, [PhBpz3] coordinates in the typical 3N,N,N fashion (C, Figure 1; MLx Fe[PhBpz3], Mo(CO)2(3-allyl), Mo(CO)2(3C7H7), ReO3, ReOCl2) via three pyrazolyl groups. In another case, only two pyrazolyl rings bind to the metal centre thereby leading to a 2N,N coordination, which is a less usual binding mode of scorpionates [8] (D, Figure 1; MLx ReO2(py)2; py pyridine). Given this background, it is of interest to gain more structural information about the ligands [Me2NBpz3] and [PhBpz3]. The aim is to develop a deeper understanding of the preferred coordination mode of the [Me2NBpz3] ion
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2 Results and Discussion 2.1 Synthesis and Spectroscopy

Upon treatment of B(NMe2)3 with 2 equiv. of Hpz and 1 equiv. of either Napz or Kpz (dimethylamino)tris(pyrazol1-yl)borates M[Me2NBpz3] (1: M Na, 2: M K, Scheme 1) are obtained. While the reaction of PhB(NMe2)2 with 2 equiv. of pyrazole (Hpz) leads to the formation of H[PhB(NMe2)pz2] [4], we found the conversion of PhB(NMe2)2 with 2 equiv. of Hpz and 1 equiv. of Kpz under similar reaction conditions as used above to give K[PhBpz3] (3, Scheme 1) in almost quantitative yield. This result clearly demonstrates that by application of the appropriate synthesis protocol it is possible to replace deliberately either one or two dimethylamino substituents. Although all compounds 13 are already known to the literature, a full characterization by 1H-, 13C- and 11BNMR spectroscopy was still lacking. Now, the complete data set is provided in the Experimental Section of this paper. A comparison of the chemical shifts determined by us with the available literature values reveals only negligible differences. According to 1H- and 13C NMR spectroscopy, all three pyrazolyl rings of each of the complexes 1 3 are magnetically equivalent on the NMR timescale (room temperature; CD3CN). This feature may be explained by assuming either a symmetric 3Npz,Npz,Npz coordination mode or fluxional behaviour of the compounds due to weak alkali metal ion complexation in polar donor solvents.

Figure 1 Possible coordination modes for tris(pyrazol-1-yl)borates: 3Npz,Npz,NNMe-[Me2NBpz3]MLx (A), 3Npz,Npz,Npz-[Me2NBpz3] MLx (B), 3N,N,N-[PhBpz3]MLx (C), 2N,N-[PhBpz3]MLx (D).

2.2 X-ray crystallography

All compounds 1 3 were characterized by X-ray crystal structure analysis. Selected distances and angles are given in the figure captions; crystal data and details of the structure determinations are summarized in Table 1. Prior to discussing the individual results, it is useful to classify the different pyrazolyl coordination modes that will be encountered (Figure 2): (1) One alkali metal ion M is located in the plane of the pyrazolyl ring and forms an adduct bond with the nitrogen lone pair (-mode; torsion angle M-N-N-B about 0). (2) Two ions M and M bind to the same nitrogen donor such that the pyrazolyl ring forms a more or less symmetrical bridge ((,)-mode; torsion angles M-N-N-B and M-N-N-B about 45). (3) One pyrazolyl ring connects two ions M and M, but now the bridge is unsymmetrical since M is coordinated via the nitrogen lone pair, whereas M binds to the -face of the aromatic heterocycle ((,)mode; torsion angles M-N-N-B and M-N-N-B about 0 and 90, respectively). Upon layering a THF solution of 1 with hexane, the compound crystallizes together with 1 equiv. of coordinated THF molecules (1THF). The polymeric solid state structure of 1THF (monoclinic, C2/c) is shown in Figure 3. Each repeat unit consists of two formula units Na[Me2NBpz3] THF and features sodium ions with distinctly different ligand spheres: Na(2) possesses a distorted octaZ. Anorg. Allg. Chem. 2006, 319324

Scheme 1 Syntheses of scorpionate ligands 1-3. (a) 1 Mpz / 2 Hpz, THF/toluene, reflux temperature.

and to see whether the phenyl substituent of [PhBpz3] always acts as an innocent spectator or whether it may establish cation- interactions with the coordinated metal ion. To this end, we report improved syntheses and crystal structure determinations of the alkali metal complexes M[Me2NBpz3] (Scheme 1; 1: M Na, 2: M K) and K[PhBpz3] (3).
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Unusual Coordination Modes of Tris(pyrazol-1-yl)borates

Figure 2 Classification of three different coordination modes of pyrazolyl rings to alkali metal ions M, M.

hedral environment made up of two scorpionate ions, each coordinated in a 3Npz,Npz,NNMe-fashion. The third pyrazolyl group of each of these ligands is attached to sodium ion Na(1) which is only tetracoordinate. It connects two pyrazolyl rings belonging to different scorpionate moieties ) and is furthermore bound to (Na(1)-N(12) 2.416(3) A two molecules of THF. The Na(1) ion lies on a twofold rotation axis dividing the angle N(12)-Na(1)-N(12)# into two halves. Na(2) is located on a centre of inversion. As a result of the structural requirements of the coordinated scorpionate ligand, the angles N(1)Na(2)N(22) 71.0(1), N(1)Na(2)N(32) 71.4(1), and N(22)Na(2)N(32) 81.2(1) are somewhat smaller than 90. The bond from the dimethylamino nitrogen atom N(1) ) to Na(2) is significantly longer (Na(2)-N(1) 2.685(3) A than the bonds from the pyrazolyl donors (Na(2)-N(22) , Na(2)-N(32) 2.418(3) A ). Moreover, the di2.385(3) A methylamino groups are in-between a planar and a fully pyramidalized configuration (sum of angles around N(1): 351.6). Both these findings indicate that the Me2N-Na inTable 1 Crystallographic data of the compounds 1THF, 2, and 3.a)
1THF formula fw colour, shape temp /K radiation cryst syst space group a /A b /A c /A / 3 V /A Z Dcalcd. /g cm3 F(000) /mm1 crystal size (mm) no. of rflns collected no. of indep rflns (Rint) data/restraints/parameter GOOF on F2 R1, wR2 (I>2(I)) R1, wR2 (all data) 3 largest diff peak and hole /e A
a)

teraction in 1THF is not a strong adduct bond, but that electrostatic attraction also plays a role. In summary, the solid state structure of 1THF establishes the coordination mode A (Figure 1) that had been proposed for the molybdenum complex [Me2NBpz3]Mo(CO)2(3-allyl) [5]. Crystals of complex 2 suitable for an X-ray crystal structure analysis were grown by layering its THF solution with hexane (orthorhombic space group, Pna21). Similar to 1THF, 2 possesses a polymeric structure in the solid state, but this time, no solvent molecules are coordinated (Figure 4). The repeat unit consists of three formula units K[Me2NBpz3]. Each potassium ion of 2 is coordinated by one scorpionate ligand in a 3Npz,Npz,NNMe fashion, reminiscent both of the binding mode of Na(2) in 1THF and of the general structural motif A (Figure 1). In the following, we will abbreviate the ligand incorporating B(1) (B(2), B(3)) as L1 (L2, L3). L1 binds to K(2), L2 to K(3), and L3 to K(1)*. Apart from K(2), L1 coordinates K(1) via the nitrogen atom N(22) ((,)-mode; K(1)-N(22) , K(2)-N(22) 2.944(4) A ) and the -face of its 3.027(5) A pz[N(31)] ring ((,)-mode; K(1)-COG(pz[N(31)]) , K(2)-N(32) 2.824(5) A ). In addition to K(3), L2 3.076 A is bound to K(2) via its pyrazolyl rings pz[N(41)] ((,) , K(3)-N(42) 2.821(5) A ) mode; K(2)-N(42) 2.891(5) A , and pz[N(61)] ((,)-mode; K(2)-N(62) 2.845(5) A K(3)-N(62) 3.412(5) A). L3 not only coordinates K(1)*, but also offers electron density of pz[N(81)] to K(3) , ((,)-mode; K(1)*-N(81) 2.800(5) A K(3) ). Moreover, the nitrogen atom COG(pz[N(81)]) 3.196 A N(72) is shared between K(1)* and K(3) ((,)-mode; , K(3)-N(72) 2.851(5) A ), and K(1)*-N(72) 3.014(5) A

2 C11H15BKN7 295.21 colourless, block 173(2) MoK, 0.71073 A orthorhombic Pna21 21.4231(18) 22.282(3) 9.1786(12) 90 4381.4(9) 12 1.343 1848 0.364 0.24 0.17 0.12 14972 6424 (0.0857) 6424 / 1 / 547 0.749 0.0469, 0.0838 0.0888, 0.0938 0.413, 0.209

3 C15H14BKN6 328.23 colourless, block 173(2) MoK, 0.71073 A monoclinic P21/n 10.1339(15) 9.0505(14) 17.211(3) 90.012(14) 1578.5(4) 4 1.381 680 0.343 0.23 0.16 0.14 15384 2718 (0.0815) 2718 / 0 / 209 1.000 0.0779, 0.2114 0.1157, 0.2308 0.729, 1.427

C15H23BN7NaO 351.20 colourless, needle 173(2) MoK, 0.71073 A monoclinic C2/c 25.078(5) 8.8168(12) 18.639(4) 112.284(14) 3813.4(12) 8 1.223 1488 0.101 0.36 0.08 0.05 13344 3418 (0.1114) 3418 / 0 / 230 0.942 0.0581, 0.1404 0.1099, 0.1651 0.283, 0.225

Crystallographic data of the structures have been deposited with the Cambridge Crystallographic Data Centre, CCDC 283476 (1THF), 283475 (2), 283477 (3). Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK.
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pz[N(91)] is bound to K(2) in the -mode (K(2)-N(92) ). In contrast to compound 1, no trend can be 2.908(5) A recognized between the length of an individual K-N bond and the nature of the donor group (Me2N vs. pz). The three ligands incorporated into the polymeric structure show only minor deviations in their bond lengths and angles. As in complex 1, the dimethylamino groups are not planar but

somewhat pyramidalized with the sums of angles around the nitrogen atoms ranging from 348.8 (N(3)) to 352.1 (N(2)). Single crystals of 3 suitable for a crystallographic analysis were obtained by layering a THF solution of the crude product with hexane. The potassium complex 3 crystallizes in the monoclinic space group P21/n; its solid state structure

Figure 3 Structure of 1THF in the crystal. H atoms omitted for clarity, vibrational ellipsoids drawn at the 30 % probability level. Selected , atomatom distances/A , bond angles/, and torsion angles/: bond lengths/A
Na(1)N(12) 2.416(3), Na(1)O(41) 2.286(3), Na(2)N(1) 2.685(3), Na(2)N(22) 2.385(3), Na(2)N(32) 2.418(3), B(1)N(1) 1.504(4), B(1)N(11) 1.570(4), B(1)N(21) 1.554(4), B(1)N(31) 1.568(4); N(12)Na(1)N(12)# 97.3(1), N(12)Na(1)O(41) 101.9(1), N(12)Na(1)O(41)# 121.7(1), O(41)Na(1)O(41)# 112.7(2), N(1)Na(2)N(22) 71.0(1), N(1)Na(2)N(32) 71.4(1), N(22)Na(2)N(32) 81.2(1), N(1)B(1)N(11) 115.9(2), N(1)B(1)N(21) 108.6(2), N(1)B(1)N(31) 107.9(3), N(11)B(1)N(21) 106.2(2), N(11)B(1)N(31) 106.1(2), N(21)B(1)N(31) 112.2(2), B(1)N(1)Na(2) 92.8(2), B(1)N(1)C(1) 120.0(3), B(1)N(1)C(2) 119.6(3), C(1)N(1)C(2) 112.0(3); B(1)N(11)N(12)Na(1) 20.6(4), B(1)N(21)N(22)Na(2) 3.9(3), B(1)N(31)N(32)Na(2) 9.9(3). #Symmetry transformation: x 1, y, z 3/2

, atomatom distances/A , bond angles/, and Figure 4 Structure of 2 in the crystal. H atoms omitted for clarity. Selected bond lengths/A torsion angles/:
K(1)N(3)# 2.941(5), K(1)N(72)# 3.014(5), K(1)N(81)# 2.800(5), K(1)N(22) 3.027(5), K(1)N(32) 2.918(5), K(1)COG(pz[N(31)]) 3.076, K(2)N(1) 2.995(5), K(2)N(22) 2.944(4), K(2)N(32) 2.824(5), K(2)N(42) 2.891(5), K(2)N(62) 2.845(5), K(2)N(92) 2.908(5), K(3)N(2) 2.906(5), K(3)N(42) 2.821(5), K(3)N(62) 3.412(5), K(3)N(12)* 2.969(5), K(3)N(72) 2.851(5), K(3)N(81) 2.909(5), K(3)COG(pz[N(81)]) 3.196, K(1)K(2) 4.504, K(1)K(3)# 4.210, K(2)K(3) 4.273, B(1)N(1) 1.493(8), B(1)N(11) 1.562(8), B(1)N(21) 1.593(8), B(1)N(31) 1.534(9), B(2)N(2) 1.507(8), B(2)N(41) 1.575(8), B(2)N(51) 1.540(7), B(2)N(61) 1.558(8), B(3)N(3) 1.490(8), B(3)N(71) 1.567(9), B(3)N(82) 1.559(8), B(3)N(91) 1.568(8); B(1)N(1)C(11) 119.5(5), B(1)N(1)C(12) 120.0(5), C(11)N(1)C(12) 110.0(5), B(2)-N(2)-C(21) 120.8(4), B(2)-N(2)-C(22) 122.3(5), C(21)-N(2)-C(22) 109.0(5), B(3)-N(3)-C(31) 119.2(5), B(3)-N(3)-C(32) 119.2(5), C(31)-N(3)-C(32) 110.4(5); B(1)-N(21)-N(22)-K(2) 33.9(5), B(1)-N(31)-N(32)-K(2) 5.4(6), B(2)-N(41)-N(42)-K(3) 52.1(5), B(2)-N(61)-N(62)K(3) 6.6(5), B(3)-N(71)-N(72)-K(1)* 32.9(5), B(3)-N(82)-N(81)-K(1)* 0.8(6); #Symmetry transformation: x1/2, y 3/2, z; *symmetry transformation: x 1/2, y 3/2, z.

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is depicted in Figure 5. Two pyrazolyl groups of the [PhBpz3] ligand coordinate to one K ion in a chelating , K(1)N(22) 2N,N mode (K(1)N(12) 2.806(5) A 2.804(5) A). The third pyrazolyl ring points away from the metal ion and is not involved in potassium coordination at all. Interestingly, the conformation of the scorpionate ligand is such that the phenyl ring presents its -face to the K ion and that a short contact between K(1) and the ipso , sum carbon atom is established (K(1)-C(41) 3.107(5) A of the ionic radius of K and the van der Waals radius of [11]). The distance between K(1) and the cencarbon: 3.4 A tre of gravity (COG) of the phenyl ring amounts to . The ligand sphere of K(1) is K(1)COG(Ph) 3.415 A 5 completed by coordination to the -faces of the pyrazolyl rings pz[N(11)#] and pz[N(21)#] with values # K(1)COG(pz[N(11) ]) and K(1)COG(pz[N(21)#]) of and 3.034 A , respectively. Thus, crystalline 3 is best 3.040 A described as coordination polymer with the pyrazolyl substituents pz[N(11)] and pz[N(21)] adopting bridging positions between two potassium ions: one ion is bound in the usual way via the nitrogen lone pairs, whereas the other interacts with the electron clouds ((,)-mode; distance between two neighbouring potassium ions: K(1)K(1)# ). 4.564 A

3 Conclusion
The alkali metal tris(pyrazol-1-yl)borates M[Me2NBpz3] (M Na (1), K (2); pz pyrazol-1-yl) and K[PhBpz3] (3) have been structurally characterized by X-ray crystallography in order to determine the coordination mode of the respective scorpionate moiety. Special emphasis was put on the question, whether the additional donor at the boron centre (NMe2, Ph) is able to compete successfully with the pyrazolyl groups for the alkali metal ion. Compounds 1 and 2 adopt a 3NpzNpzNNMe- instead of the usual 3NpzNpzNpz binding mode. The M-NNMe ) contacts in the sodium complex 1 are signifi(2.685(3) A , cantly longer than the M-Npz bonds (2.385(3) A 2.418(3) A). However, these differences are leveled out in the potassium salt 2. In both cases 1 and 2, the configuration of the dimethylamino groups is close to planarity (sum of angles around nitrogen close to 350). Even though not only the Npz atoms but also the NNMe atoms are thus approximately sp2 hybridized, the B-NNMe bonds are significantly shorter than the B-Npz bonds. In K[PhBpz3] (3), the ligand chelates the potassium ion through two pyrazolyl rings. While the third pyrazolyl ring just acts as a dangling substituent, a short M-phenyl distance of K(1)C(41)

Figure 5 Structure of 3 in the crystal. H atoms omitted for clarity, vibrational ellipsoids drawn at the 50 % probability level. Selected bond , atomatom distances/A , bond angles/, and torsion angles/: lengths/A
K(1)N(12) 2.806(5), K(1)COG(pz[N(11)#]) 3.040, K(1)N(22) 2.804(5), K(1)COG(pz[N(21)#]) 3.034, K(1)C(41) 3.107(5), K(1)COG(Ph) 3.415, K(1)LSPL(Ph) 3.086, B(1)N(11) 1.569(7), B(1)N(21) 1.582(7), B(1)N(31) 1.541(7), B(1)C(41) 1.616(6), B(1)LSPL(Ph) 0.196, K(1)K(1)# 4.564; N(12)K(1)N(22) 68.0(1), N(12)-K(1)-C(41) 61.3(1), N(22)-K(1)-C(41) 62.8(1), N(11)B(1)N(21) 108.2(4), N(11)B(1)N(31) 109.7(4), N(11)B(1)C(41) 110.6(4), N(21)B(1)N(31) 108.3(4), N(21)B(1)C(41) 111.1(4), N(31)B(1)C(41) 108.9(4); B(1)N(11)N(12)K(1) 2.7(5), B(1)N(21)N(22)K(1) 6.4(5). #Symmetry transformation: x 1/2, y 1/2, z 1/2. Z. Anorg. Allg. Chem. 2006, 319324 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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is observed. We may therefore conclude that in 3.107(5) A scorpionate chemistry, seemingly innocent spectator substituents like the phenyl group may replace a pyrazolyl ring in metal coordination.

4 Experimental Section
General Considerations. All reactions and manipulations of air-sensitive compounds were carried out in dry, oxygen-free nitrogen using standard Schlenk ware. Solvents were freshly distilled under Ar from Na-benzophenone (THF, toluene, n-hexane) or stored over molecular sieves prior to use (CD3CN). NMR: Bruker Avance 4A 400, Bruker AMX 250, Bruker DPX 250 spectrometers with calibration against the solvent signal (CD3CN: 1H NMR 1.93 ppm, 13 C NMR 1.3 ppm). 11B NMR spectra are reported relative to external BF3 Et2O. All NMR spectra were run at ambient temperature. Abbreviations: s singlet; d doublet; vtr virtual triplet; m multiplet; n.r. multiplet expected in the 1H NMR spectrum but not resolved; n.o. signal not observed, pz pyrazol-1-yl, THF tetrahydrofuran. Bis(dimethylamino)phenylborane was prepared according to a literature procedure [12]. Tris(dimethylamino)borane and pyrazole were purchased from Aldrich. Preparation of Na[Me2NBpz3] (1): To a solution of freshly prepared sodium pyrazolide (0.69 g, 7.71 mmol) and pyrazole (1.05 g, 15.42 mmol) in THF (10 mL) were added with stirring neat tris(dimethylamino)borane (1.10 g, 7.71 mmol) and toluene (10 mL). The mixture was heated to reflux temperature for 8 h. After cooling to r.t., a white solid precipitated which was filtered through a frit, washed with hexane (10 mL) and dried in vacuo. X-ray quality crystals of 1THF were grown by layering a THF solution of 1 with hexane (volume ratio 1:3). Yield of 1THF: 1.89 g (5.38 mmol, 70 %). 1H NMR (250.1 MHz, CD3CN): 2.16 (s, 6H, NMe2), 6.10 (dd, 3JHH 2.2 Hz, 3JHH 1.6 Hz, 3H, pzH-4), 7.48 (dd, 3JHH 2.2 Hz, 4JHH 0.6 Hz, 3H, pzH-3 or 5), 7.54 (dd, 3JHH 1.6 Hz, 4 JHH 0.6 Hz, 3H, pzH-5 or 3). 13C NMR (62.9 MHz, CD3CN): 39.1 (NMe2), 103.8 (pzC-4), 134.9 (pzC-3 or 5), 140.1 (pzC-5 or 3). 11 B NMR (128.4 MHz, CD3CN): 2.7 (h1/2 30 Hz). 1 is a derivative of Me2NBpz3H prepared by Niedenzu et al. [4]. Thus, no elemental analysis was carried out. Preparation of K[Me2NBpz3] (2): Freshly prepared potassium pyrazolide (1.11 g, 10.50 mmol) was added to a solution of tris(dimethylamino)borane (1.50 g, 10.49 mmol) and pyrazole (1.43 g, 21.00 mmol) in THF (20 mL) and toluene (20 mL). The mixture was heated to reflux temperature for 8 h, the solvent was evaporated and the resulting white microcrystalline solid dried in vacuo. Yield: 3.07 g (10.40 mmol, 99 %). X-ray quality crystals of 2 were grown by layering a THF solution with hexane (volume ratio 1:3). 1H NMR (250.1 MHz, CD3CN): 2.17 (s, 6H, NMe2), 6.08 (vtr, 3JHH 1.8 Hz, 3H, pzH-4), 7.42 (d, 3JHH 1.8 Hz, 3H, pzH3 or 5), 7.52 (n.r., 3H, pzH-5 or 3). 13C NMR (62.9 MHz, CD3CN): 37.9 (NMe2), 102.3 (pzC-4), 133.2 (pzC-3 or 5), 138.2 (pzC-5 or 3). 11 B NMR (128.4 MHz, CD3CN): 2.5 (h1/2 30 Hz). 2 is a derivative of Me2NBpz3H prepared by Niedenzu et al. [4]. Thus, no elemental analysis was carried out. Preparation of K[PhBpz3] (3): To a solution of bis(dimethylamino)phenylborane (0.53 g, 3.01 mmol) and pyrazole (0.40 g, 6.02 mmol) in toluene (20 mL) and THF (10 mL) was added with stirring freshly prepared potassium pyrazolide (0.32 g, 3.01 mmol). The mixture was heated to reflux temperature for 8 h. The solvent was evaporated and the resulting white precipitate dried in vacuo. Yield: 0.96 g (2.92 mmol, 97 %). X-ray quality crystals of 3 were grown 324

by layering a THF solution with hexane (volume ratio 1:3). 1H NMR (250.1 MHz, CD3CN): 6.10 (dd, 3JHH 2.1 Hz, 3JHH 1.5 Hz, 3H, pzH-4), 7.03-7.06 (m, 2H, PhHo), 7.14-7.20 (m, 3H, PhHm,p), 7.22 (dd, 3JHH 2.1 Hz, 4JHH 0.6 Hz, 3H, pzH-3 or 5), 7.51 (dd, 3JHH 1.5 Hz, 4JHH 0.6 Hz, 3H, pzH-5 or 3). 13C NMR (62.9 MHz, CD3CN): 103.8 (pzC-4), 127.1 (PhCp), 127.6 (PhCm), 134.7 (PhCo), 135.4 (pzC-3 or 5), 140.1 (pzC-5 or 3). 11B NMR (128.4 MHz, CD3CN): 1.7 (h1/2 90 Hz). Since 3 is the potassium salt of a well-known ligand [6], no elemental analysis was carried out.

X-ray crystal structure determinations of 1-3

Data collection was performed on a Stoe-IPDS-II two-circle diffractometer with graphite-monochromated MoK radiation. An empirical absorption correction with the MULABS option [13] in the program PLATON [14] was performed. The structure was solved by direct methods [15] and refined with full-matrix leastsquares on F2 using the program SHELXL-97 [16]. Hydrogen atoms were placed on ideal positions and refined with fixed isotropic displacement parameters using a riding model. For 2, the absolute structure was determined: Flack x parameter 0.03(5). The crystal of 3 showed pseudo-translational symmetry of x 0.5, y, z 0.5. Therefore, the reflections with (h l) odd number have been given a different weight than the others. CCDC reference numbers: 283476 (1THF), 283475 (2), 283477 (3). Acknowledgement. The authors are grateful to the Deutsche Forschungsgemeinschaft (DFG) and the Fonds der Chemischen Industrie (FCI) for financial support.

References
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