Collect. Czech. Chem. Commun. 2007, 72, 599-608

Reactions of Bis(phenyldiazenido)rhenium Complex [ReBr2(NNPh)2(PPh3)2]Br with Carbon Monoxide and Alk-1-ynes

Maria Teresa A. R. S. da Costa, Maria Fátima C. Guedes da Silva, João J. R. Fraústo Da Silva and Armando J. L. Pombeiro*

Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal


The conversion of the bis(diazenido) complex [ReBr2(NNPh)2(PPh3)2]Br (1) to the mono(diazenido) complex [ReBr3(NNPh)(PPh3)2] (2) is promoted by alk-1-ynes, whereas the reaction with CO leads to the mixed dicarbonylmono(diazenido) Re(III) species [ReBr(CO)2- (NNPh)(PPh3)2]Br (3). Both reactions are suggested to occur via related pathways involving a nucleophilic displacement of one of the diazenide ligands by Br-. Reduction of the phenyldiazenide ligand in 2 occurs in the attempted reaction with HC≡CPh to give the nitrido complex [ReBr2(N)(PPh3)2] (4) and the bis(diazenido) species [ReBr2(NNPh)2(PPh3)2] (5) and [ReBr(NNPh)2(PPh3)2] (6).

Keywords: Alkynes; Carbonyl complexes; Rhenium; Diazenido complexes; Diazenes; N ligands; Coordination chemistry.

References: 50 live references.