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Agostic Interactions from a Computational Perspective: One Name, Many Interpretations

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Principles and Applications of Density Functional Theory in Inorganic Chemistry II

Part of the book series: Structure and Bonding ((STRUCTURE,volume 113))

Abstract

The agostic bond defines an intramolecular interaction where a σ bond is geometrically close to an electron deficient centre (often a transition metal). The computational studies on this energetically weak interaction are reviewed and discussed. Various types of σ bonds have been considered (C-H, C-C, Si-H, Si-C, B-H). It is suggested that a C-X bond in which X carries a lone pair should preferably not be viewed as agostic. The factors that contribute to his occurrence are discussed. In particular, the agostic interaction is very sensitive to steric effects. Explanations based on molecular orbital analysis, electron delocalization and topological analysis of the electron density are presented.

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Acknowledgements

Part of the work presented here has resulted from long-term collaborations between the authors and a number of experimental and computational chemists throughout the world, as well as from the work of previous and present co-workers. It is our pleasure to thank R.A. Andersen (Berkeley), M. Besora (UA Barcelona), R. Bosque (Barcelona), K.G. Caulton (Indiana), R.H. Crabtree (Yale), E.R. Davidson (Indiana), H. Gérard (Paris VI), Y. Jean (Paris-Sud, Ecole Polytechnique), M.F. Lappert (Sussex), A. Lledós (UA Barcelona), F. Maseras (Tarragona), J.E. McGrady (York), M. Etienne (LCC CNRS, Toulouse), L. Perrin (Montpellier 2), L. Maron (Paul Sabatier, Toulouse), G. Ujaque (UA Barcelona).

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  1. Laboratoire de Structure et Dynamique des Systèmes Moléculaires et Solides (UMR 5636), cc14, Université Montpellier 2, 34095, Montpellier Cedex 05, France

    Eric Clot & Odile Eisenstein

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Clot, E., Eisenstein, O. (2004). Agostic Interactions from a Computational Perspective: One Name, Many Interpretations. In: Principles and Applications of Density Functional Theory in Inorganic Chemistry II. Structure and Bonding, vol 113. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b97940

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