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Localization and Delocalization in Quantum Chemistry pp 325–363Cite as

Localized Analysis of the Stereospecificity of Concerted Reactions

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Part of the book series: Localization and Delocalization in Quantum Chemistry ((LDQC,volume 2))

Abstract

It is pointed out that in the delocalized Woodward-Hoffmann demonstration of the concerted reactions stereospecificity (i) some energetical hypotheses concerning the transition state region are implicitly required, (ii) the MO’s correlations are ambiguous if no spatial criterion is. taken into account, and (iii) the demonstration itself and its application to real unsymmetric systems require some relocalization of the canonical MO’s. Using a perturbative configuration interaction in a basis of localized orbitals (PCILO), one tries to analyze the energy of the transition state region. The stereospecificity for a n-bond polyenic chain results from a nth order correction in the perturbation expansion representing circular delocalization effects around the reacting circle. The stereospecificity is linked directly to the parity of n without any symmetry consideration, but the energy difference between the two modes may vanish when n increases. PCILO-CNDO/2 and ab-initio numerical calculations for n = 2 support the theoretical analysis.

The ab-initio approach allows a distinction between the σ, π and σπ effects and confirms that the π electronic factors are responsible for the stereospecificity However a stereospecific short range repulsion effect also appears, due to the overlap between the π bonds. The localized demonstration of the Woodward-Hoffmann rules is generalized to cycloadditions and sigmatropic reactions.

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Authors and Affiliations

  1. Laboratoire de Biochimie Théorique associé au CNRS, Institut de Biologie Physico-Chimique, 75005, Paris, France

    J. Langlet

  2. Laboratoire de Physique Quantique, Université Paul Sabatier, 31077, Toulouse, France

    J. P. Malrieu

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  1. Centre de Mécanique Ondulatoire Appliquée du C.N.R.S., 23, rue du Maroc, Paris 19ème, France

    Odilon Chalvet  & Raymond Daudel  & 

  2. Institut de Biologie Physico-Chimique, 13, rue Pierre et Marie Curie, Paris 5ème, France

    Simon Diner  & Jean Paul Malrieu  & 

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© 1976 D. Reidel Publishing Company, Dordrecht, Holland

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Langlet, J., Malrieu, J.P. (1976). Localized Analysis of the Stereospecificity of Concerted Reactions. In: Chalvet, O., Daudel, R., Diner, S., Malrieu, J.P. (eds) Localization and Delocalization in Quantum Chemistry. Localization and Delocalization in Quantum Chemistry, vol 2. Springer, Dordrecht. https://doi.org/10.1007/978-94-010-1456-4_19

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  • DOI: https://doi.org/10.1007/978-94-010-1456-4_19

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