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

Flükiger, Peter
Published in Comments on Inorganic Chemistry. 1992, vol. 14, no. 1, p. 27-62
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 reactivityReaction potentialsMolecular modelinExtended-Huumlckel theoryMolecular graphicsSemiempirical quantum chemistry
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Research group Groupe Weber
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WEBER, Jacques et al. Development and applications of an extended-Hückel-based reactivity index for organometallic complexes. In: Comments on Inorganic Chemistry, 1992, vol. 14, n° 1, p. 27-62. https://archive-ouverte.unige.ch/unige:2915

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Deposited on : 2009-09-21

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