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Scientific article
English

Development and applications of an extended-Hückel-based reactivity index for organometallic complexes

Publication date1992
Abstract

A new formalism has been developed to evaluate from extended-Huumlckel wave-functions the intermolecular interaction energy Eint between an organometallic substrate S and a model electrophile or nucleophile reactant R. Calculated as the sum of electrostatic, charge-transfer and exchange-repulsion components, Eint is used as a local reactivity index to interpret and predict the regio- and stereoselectivity of electrophilic and nucleophilic addition reactions to organometallics. The methodology developed incorporates molecular graphics as an important ingredient, as the reactivity index is represented using either: (i) a mapping onto the molecular surface by S by means of a color code or (ii) the generation of 3D isoenergy contour surfaces. This model is shown to be able to rationalize the activation of a benzene ring by complexation to the Cr(CO)3 moiety and also to describe adequately the sequential addition of a carbanion nucleophile and of an electrophile to (η6-benzene)tricarbonylchromium derivatives.

Keywords
  • Organometallic reactivity
  • Reaction potentials
  • Molecular modelin
  • Extended-Huumlckel theory
  • Molecular graphics
  • Semiempirical quantum chemistry
Research group
Citation (ISO format)
WEBER, Jacques et al. Development and applications of an extended-Hückel-based reactivity index for organometallic complexes. In: Comments on modern chemistry. Part A, Comments on inorganic chemistry, 1992, vol. 14, n° 1, p. 27–62.
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Article (Published version)
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Identifiers
  • PID : unige:2915
ISSN of the journal0260-3594
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