期刊
INORGANICA CHIMICA ACTA
卷 310, 期 2, 页码 183-190出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/S0020-1693(00)00285-1
关键词
CO dehydrogenase; crystal structures; hydrogenases; ligand field; nickel complexes; schiff base complexes
Four new nickel(II) complexes of dissymmetric tetradentate ligands, containing mixed-ligand donor sets of NSNS or NSNO, have been synthesized. These complexes were prepared by facile template reactions of the appropriate aldehyde and amine in the presence of [Ni(H2O)(6)](BF4)(2), resulting directly in the desired nickel compounds. The nickel compounds were characterized by analytical, spectroscopic and electrochemical methods. The structures of [Ni(pyzs)]BF4, [Ni(pyrs)]BF4 and [Ni(pyzo)]BF4 (see Scheme 1) have been determined by single-crystal X-ray crystallography, showing the geometry of the nickel ion to be square-planar. Vis-NIR spectra show that the phenolate-containing complexes [Ni(pyzo)]BF4 and [Ni(pyro)]BF4 (see Scheme 1) are essentially square-planar in nitromethane, but tetragonal octahedral in methanol, whereas the thiophenolate-containing compounds [Ni(pyzs)]BF4 and [Ni(pyrs)]BF4 remain square-planar in both solvents. Titration of the thiophenolate-containing complexes with 1-methylimidazole results in diamagnetic five-coordinated complexes. Electrochemistry shows quasi-reversible reductions to Ni(I) to occur for [Ni(pyzo)]BF4, [Ni(pyrs)]BF4 and [Ni(pyro)]BF4. (C) 2000 Elsevier Science B.V. All rights reserved.
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