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Studies of two interrelated series of triiridatrithia-cyclohexane and trimetallatrithia (or trioxo)-adamantane rhodium and iridium complexes
Authors:J Devillers  A Maisonnat  R Poilblanc
Institution:(1) Centre d’Elaboration de Matériaux et d’Etudes Structurales du CNRS, UPR 8011, 29, rue Jeanne Marvig, 31055 Toulouse Cedex, France;(2) Laboratoire de Chimie de Coordination du CNRS, UPR 8241, 205 route de Narbonne, 31077 Toulouse Cedex, France
Abstract:From a comparativereview on the two title series of compounds, the first part of the paper describes the most salient structural and reactivity properties of these trimetallic complexes, including metal-metal bond formation, conformational changes, enantio, and diastereomorphism. The second part presentsnew results which extend the comparison to a series of trimetallatrioxo adamantane complexes. The single crystal X-ray diffraction of the parent compound Rh3{μ 3−(OCH2)3CCH3}(CO)6]—a derivative of the commercially available tripod ligand 1,1,1tris (oxomethyl)ethane—is reported together with its crystal packing which is compared to that of its sulfido analog. The paper includes a discussion of the nucleophilic and electrophilic properties of the trimetalla trioxo adamantane rhodium complexes, based on semi-empirical extended Hückel calculations Dedicated to Professor Yves Jeannin on the occasion of his 65 th birthday.
Keywords:Trimetallic complexes  tripodal ligands  rhodium  iridium  silver  oxidative addition  metal-metal bond  threefold vacant sites  crystal structure  E  H  M  O  calculations
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