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DOI: 10.1039/A800898A (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 2405-2410

Syntheses and characterization of phenyldiazenido and mixed phenyldiazenido–isocyanide complexes of rhenium. Crystal structure of [ReBr2(NNPh)2(PPh3)2]

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M. Teresa A. R. S. da Costa, Jonathan R. Dilworth, M. Teresa Duarte, João J. R. Fraústo da Silva, Adelino M. Galvão and Armando J. L. Pombeiro

Abstract

The complex [ReBr2(NNPh)2(PPh3)2]Br 1, prepared by bromination of [ReCl(NNPh)2(PPh3)2], was reduced, in thf or acetone, to the paramagnetic phenyldiazenido-complex [ReBr2(NNPh)2(PPh3)2] 2 and its acetone solvate 2·Me2CO (formed in the presence of HSC6H2Pri3-2,4,6 or CNMe), and converted spontaneously (via a conceivable nucleophilic displacement at phenyldiazenide) into [ReBr3(NNPh)(PPh3)2] 3 from which 2 can also be derived. The molecular structure of 2 has been determined by X-ray diffraction analysis which indicates that one of the diazenide ligands is doubly bent and the other singly bent, each being trans to a bromide ligand and exerting a significant trans influence. Complexes 1–3 react with isocyanides to give the reduced mixed diazenido–isocyanide complexes [ReBr2(NNPh)(CNR)(PPh3)2] (R = Me 4 or C6H4Cl-4 5), [ReBr2(NNPh)(CNMe)2(PPh3)] 6 or [ReBr(NNPh)(CNMe)2(PPh3)2] 7.

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