In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2003, No. 11 ( 2003-06), p. 2059-2070
Abstract:
The thallium( I ) salts of tris(pyrazolyl)methanesulfonate (Tpms) and tris(3‐ tert ‐butylpyrazolyl)methanesulfonate (Tpms t Bu ) have been used to prepare the following complexes: [(Tpms t Bu )ZnX] [X = Cl ( 1a ), Br ( 1b ), I ( 1c ), Et ( 3 ), OAc ( 5a )], [(Tpms t Bu )NiX] [X = Cl ( 2a ), Br ( 2b )], [(Tpms t Bu )CoCl(Hpz t Bu )] ( 3 ), [(Tpms t Bu )Zn(μ‐OAc)(μ‐OH)Zn(Tpms t Bu )] ( 5b ), [(Tpms t Bu )Cu(CO)] ( 6a ), and [(Tpms)Cu(CO)] ( 6b ). The solid‐state structures of 1b , 2a , 3 , and 5b have been determined by X‐ray analysis. The optical spectra of 2a and 3 were investigated by means of the angular overlap model to elucidate their electronic structures in view of the underlying molecular geometries. Variable‐temperature NMR and IR spectroscopic studies show that Tpms and Tpms t Bu can act as N,N,N and N,N,O ligands. Both coordination modes are present in solution for the zinc complexes 1a , b and the copper carbonyl complexes 6a , b . The N,N,O bonding mode is entropically favoured in solution. For the nickel complexes 2a , b , the Tpms t Bu ligand acts as a tripodal nitrogen ligand in the solid state and in solution. For the dinuclear zinc complex 5b , one of the Tpms t Bu ligands acts as an N,N,O ligand and one as an N,O ligand. Complex 5b is one of the very few structural models of the dinuclear zinc enzymes phospholipase C and phosphotriesterase. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2003:11
DOI:
10.1002/ejic.200200604
Language:
English
Publisher:
Wiley
Publication Date:
2003
detail.hit.zdb_id:
1475009-0
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