Please use this identifier to cite or link to this item: http://repositorio.unicamp.br/jspui/handle/REPOSIP/72955
Type: Artigo de periódico
Title: X-ray molecular structures and multinuclear NMR studies of the tetranuclear iridium. clusters [Ir-4(CO)(7)(mu(4)-eta(3)-PhCCH)CCPh)-(mu-PPh2)(3)] and [Ir-4(CO)(7)(mu(3)-eta(2)-HCCPh)(eta(1)-CCPh)(mu-PPh2)(3)]
Author: Araujo, MH
Pereira, RMS
Vargas, MD
Braga, D
Grepioni, F
Abstract: The reaction of [HIr4(CO)(10)(mu-PPh2)] with two equiv. of Ph2PC&3bond; CPh produced [HIr4(CO)(8)(Ph,PC&3bond; CPh)(2)(mu-PPh2)] (1) in quantitative yield. Mild thermolysis of 1 gave [Ir-4(CO)(7)(mu(4)-eta(3)-PhCC(H)CCPh)(mu-PPh2)(3)] (2) and [Ir-4(CO)(7)(mu(3)-eta(2)-HCCPh)(eta(1-)CCPh)(eta(1)-PPh2)(3)] (3) in good yields. These compounds were characterized with analytical and spectroscopic data including H-1, C-13 and P-31 NMR (1 and 2D) spectroscopy, and their molecular structures were established by X-ray diffraction studies. The metal frameworks of 2 and 3 are similarly constituted of a spiked metal triangle; in both clusters the seven CO ligands are terminally bound and the three -PPh2 ligands span two consecutive Ir-Ir bonds and an open edge. The difference between the two structures is that compound 2 contains a butadienic chain, mu(4)-eta(3)-PhCC(H)CCPh, interacting with all four iridium atoms, whereas compound 3 bears two fragments of this ligand, i.e. a phenylacetylene capping a triangular face and a terminally bound phenylacetylide bonded to the fourth atom of the cluster. Although these two fragments are directed in the appropriate fashion to interact further and generate the chain of compound 2, they do not undergo condensation under thermolytic conditions. (c) 2005 Elsevier B.V. All rights reserved.
Subject: tetrairidium clusters
acetylide
C-C coupling
X-ray molecular structure
Country: Suíça
Editor: Elsevier Science Sa
Rights: fechado
Identifier DOI: 10.1016/j.jorganchem.2005.07.032
Date Issue: 2005
Appears in Collections:Unicamp - Artigos e Outros Documentos

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