en
Scientific article
English

The modeling of nucleophilic and electrophilic additions to organometallic complexes using molecular graphics techniques

Published inJournal of computer-aided molecular design, vol. 2, no. 3, p. 235-253
Publication date1988
Abstract

A new formalism has been developed in order to evaluate intermolecular interaction energies for inorganic and organometallic complexes in the framework of the extended Hückel method. In order to provide the shortest possible response time on an interactive computer graphics facility, this model should require the minimum amount of computer time, which explains why approximate procedures are used to evaluate electrostatic, charge transfer and exchange repulsion components. When applying this model to typical examples of electrophilic addition reactions to organometallic complexes, it is found that it is essential to take account of charge transfer interactions, the electrostatic component alone being not sufficient, even qualitatively, for a proper description of the reaction mechanism. The results, presented as color-coded dot molecular surfaces, show a very good agreement with experiment as to the site of attack, namely (i) on metal for the electrophilic attack on Fe(cp)2, Fe(CO)5 and X(cp)(CO)2, X=Co, Rh; (ii) on the cp ligand for the nucleophilic attack on Co(cp)2 + and Rh(cp)2 +; (iii) on bz for the nucleophilic attack on Fe(cp)(bz)+. Finally, modellizations of the nucleophilic attack on a coordinated olefin and of the relation between structure and acidic properties of zeolites are presented and discussed.

Keywords
  • Intermolecular interactions
  • Extended Hückel
  • Dot surfaces
  • Molecular properties
  • Reactivity
Research group
Citation (ISO format)
WEBER, Jacques et al. The modeling of nucleophilic and electrophilic additions to organometallic complexes using molecular graphics techniques. In: Journal of computer-aided molecular design, 1988, vol. 2, n° 3, p. 235–253. doi: 10.1007/BF01531997
Identifiers
ISSN of the journal0920-654X
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