LIGAND-EXCHANGE REACTIONS OF RECL4(PPH3)(2), REOCL3(PPH3)(2) AND NICL2(PPH3)(2) WITH ACETYLACETONE THIOBENZOYLHYDRAZONE - AN UNEXPECTED TEMPLATE REACTION AT THE REO3- MOLECULAR-STRUCTURES OF THE RESULTING OXORHENIUM(V) AND NICKEL-COMPLEXES( CORE )

The ligand exchange reactions of ReCl4(PPh3)(2), ReOCl3(PPh3)(2) and N iCl2(PPh3)(2) with acetylacetone thiobenzoylhydrazone have been studie d. An unexpected template reaction at the ReO3+ core forming the new t etradentate triacidic ligand triacetylmethane bis(thiobenzoylhydrazone ) will be described and discussed. The final products were characteriz ed by elemental analysis, mass spectroscopy, H-1 NMR, IR, W-VIS spectr oscopy and X-ray structural analysis. [Acetylacetone thiobenzoylhydraz onato(2-)]chloro-oxorhenium(V) was isolated as an intermediate. The cr ystal structures have been determined cf [triacetylmethane bis( thiobe nzoylhydrazonato) (3-)-S,S',N,N'] oxorhenium(V) C21H19N4O2S2Re, monocl inic P2(1)/m, a = 7.451 (1), b = 11.262(3), c = 12.639(4) Angstrom, be ta = 90.66(2)degrees, Z = 2, R-1 = 0.0445, and [acetylacetone obenzoyl hydrazonato(2-)]-triphenylphosphane-nickel (II) C30H27N2OSPNi, orthorh ombic 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.