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Tris(pyrazolyl)methanesulfonates: More Than Just Analogues of Tris(pyrazolyl)borate Ligands; N,N,N‐, N,N,O‐, and Other Coordination Modes
Author(s) -
Kläui Wolfgang,
Berghahn Michael,
Frank Walter,
Reiß Guido J.,
Schönherr Thomas,
Rheinwald Gerd,
Lang Heinrich
Publication year - 2003
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200200604
Subject(s) - chemistry , ligand (biochemistry) , tris , zinc , crystallography , stereochemistry , medicinal chemistry , organic chemistry , receptor , biochemistry
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)