Ligand exchange reactions of ReCl4(PPh3)(2), ReOCl3(PPh3)(2) and NiCl2(PPh3)(2) with acetylacetone thiobenzoylhydrazone. An unexpected template reaction at the ReO3+ core. Molecular structures of the resulting oxorhenium(V) and nickel complexes

摘要

The ligand exchange reactions of ReCl4(PPh3)(2), ReOCl3(PPh3)(2) and NiCl2(PPh3)(2) with acetylacetone thiobenzoylhydrazone have been studied. An unexpected template reaction at the ReO3+ core forming the new tetradentate triacidic ligand triacetylmethane bis(thiobenzoylhydrazone) will be described and discussed. The final products were characterized by elemental analysis, mass spectroscopy, H-1 NMR, IR, W-VIS spectroscopy and X-ray structural analysis. [Acetylacetone thiobenzoylhydrazonato(2-)]chloro-oxorhenium(V) was isolated as an intermediate. The crystal structures have been determined cf [triacetylmethane bis( thiobenzoylhydrazonato) (3-)-S,S',N,N'] oxorhenium(V) C21H19N4O2S2Re, monoclinic P2(1)/m, a = 7.451 (1), b = 11.262(3), c = 12.639(4) Angstrom, beta = 90.66(2)degrees, Z = 2, R-1 = 0.0445, and [acetylacetone thiobenzoylhydrazonato(2-)]-triphenylphosphane-nickel (II) C30H27N2OSPNi, orthorhombic Pbca, a = 16.658(2), b = 14.725(2), c = 21.950(2) Angstrom, Z = 8, R-1 = 0.0283. (C) 1998 Elsevier Science S.A. All rights reserved. [References: 28]