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Type: Artigo de periódico
Title: Oxidative addition reactions of I-2 with [HIr4(CO)(10-n)(PPh3)(n)(mu-PPh2)] (n=1 and 2) and crystal and molecular structure of [HIr4(mu-I)(2)(CO)(7)(PPh3)(mu-PPh2)]
Author: Braga, D
Grepioni, F
Vargas, MD
Ziglio, CM
Abstract: The reactions of the cluster compounds [Hlr(4)(CO)(10-n)(PPh3)(n) (mu-PPh2)] [n = 0, (1); 1, (2) and 2, (3)] with I-2 have been investigated. Compound 1 does not react, however, the presence of PPh3 in place of CO ligand(s) activates the cluster. Both compounds 2 and 3 react with I-2 under mild conditions to give [Hlr(4)(mu-I)(2)(CO)(7)(PPh3)(mu-PPh2)] (4), as the result of oxidative addition of I-2 and dissociation of two CO ligands, or one CO and one PPh3 ligands, respectively. The molecular structure of 4, determined by an X-ray diffraction study, exhibits a butterfly arrangement of iridium atoms with the wings spanned by amu-PPh2 ligand, the hinge bridged by amu-H ligand, two hinge to wing tip edges bridged by iodine atoms and all metal atoms bearing two CO ligands, with the exception of one of the hinge atoms that contains a CO and a PPh3 ligands. This cluster exhibits the shortest average Ir-Ir bond length [2.698(2) Angstrom] observed so far for a derivative of 1 and this is in accord with the relatively high average oxidation state of its metal atoms (+1) for a carbonyl cluster compound.
Subject: iridium cluster
oxidative addition
X-ray molecular structure
Country: Brasil
Editor: Soc Brasileira Quimica
Rights: aberto
Identifier DOI: 10.1590/S0103-50532002000500024
Date Issue: 2002
Appears in Collections:Unicamp - Artigos e Outros Documentos

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