A. Dołega et al. / Inorganica Chimica Acta 357 (2004) 461–467
467
z
i.e., N-methylimidazole, pyridine, a-picoline and 2,4-
lutidine served as nitrogen donors.
In reactions of [Zn{l-SSi(OBu )3}(acac)]2 with het-
erocyclic ligands we easily obtained two types of com-
plexes:
IR spectra of all synthesized compounds as well as
detailed crystallographic data are available on request
from Anna Dołega.
t
z
•
•
tetracoordinated with two thiolate groups and two
molecules of heterocyclic ligands,
penta-coordinated with two thiolate groups, one mol-
ecule of heterocyclic ligand and additional weak co-
ordination of zinc by two oxygen atoms from tert-
butoxy groups.
References
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1] B. Becker, A. Dołega, A. Konitz, W. Wojnowski, Polyhedron 20
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[
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[Zn{l-SSi(OBu )3}(acac)]2 with pyridine and N-methyl-
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from [{(OBu ) SiS}(H O) Zn{l-SSi(OBu ) }Zn (acac)
{
methylimidazole, a-picoline, 2,4-lutidine.
We suppose that the structure of complexes 2 and
[
334 (2002) 25.
[6] B. M u€ ller, A. Schneider, M. Tesmer, H. Varenkamp, Inorg.
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t
t
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3
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t
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3 3 2
[
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4
, where zinc is actually penta-coordinated though two
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Chem. 40 (2001) 2212.
Zn–O interactions are weak and differ in length, could
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centre of alcohol dehydrogenase. We are aware that
up to now there is no evidence that a molecule of
water remains bonded to zinc during the catalytic
cycle. Moreover AM1 and PM3 calculations indicate
that water moves away from zinc ion when substrate
[
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[
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z
Anorg. Allg. Chem. 627 (2001) 280.
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(
ethanol) is being bonded [26]. Nevertheless in com-
2
0 (2001) 2567.
plexes 2 and 4 zinc definitely tends to complete its
coordination sphere with two oxygen atoms. The re-
sults of our work are in agreement with the sugges-
tions of Zhang et al. [27] that zinc in neutral thiolate
complexes shows a tendency to form penta-coordi-
nated structures.
Among known penta-coordinated zinc complexes of
nitrogen, oxygen and sulfur ligands listed in the Cam-
bridge Crystallographic Data File we have not found
15] B. Becker, W. Wojnowski, K. Peters, E.-M. Peters, H.G. von
Schnering, Inorg. Chim. Acta 214 (1993) 9.
[
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ꢀ
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z
[20] G.M. Sheldrick, Acta Crystallogr., Sect. A 46 (1990) 467.
[
21] G.M. Sheldrick, SHELXL-97, Program for the Solution and the
Refinement of Crystal Structures from Diffraction Data, Univer-
sity of G o€ ttingen, G o€ ttingen, Germany, 1997.
1
complexes with ZnNO2S2 core.
[
22] M. Bochmann, G.C. Bwembya, R. Grinter, A.K. Powell, K.J.
Webb, M.B. Hursthouse, K.M. Abdul Malik, M.A. Mazid, Inorg.
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[
[
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4
. Supplementary material
(
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[
[
[
25] X.-M. Chen, Z.-T. Xu, X.-C. Huang, J. Chem. Soc., Dalton
Trans. (1994) 2331.
Structures of complexes 1, 2, 4, and 5 are deposited in
Cambridge Crystallographic Data File with the following
numbers: complex 1 – CCDC 205888, complex 2 – CCDC
26] S.A.M. Vanhommering, R.J. Meier, L.A.Æ. Sluyterman, J. Mol.
Struct. (Theochem.) 364 (1996) 33.
205889, complex 4 – CCDC 205886, complex 5 – CCDC
05887.
27] C. Zhang, R. Chadha, H.K. Reddy, G.N. Schrauzer, Inorg.
Chem. 30 (1991) 3865.
2
1
The Cambridge Crystallographic Data File reports 57 structures of
penta-coordinated Zinc complexes bearing at least one sulfur, one
nitrogen and one oxygen ligand.