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Spin-coupled study of addition reactions of singlet dihalocarbenes with ethene

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JournalINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
DatePublished - 20 Jun 2004
Issue number5
Volume98
Number of pages8
Pages (from-to)465-472
Original languageEnglish

Abstract

Modern valence bond theory, in its spin-coupled form, is used to examine the electronic rearrangements that take place during the gas-phase additions of singlet CF2 and of singlet CCl2 to ethene. Both reactions are found to follow homolytic pathways, during which the ethene pi-bond breaks and the orbitals that were originally involved in this bond interact with the singlet orbital pair on the carbene. The formation of the two new sigma bonds that close the cyclopropane ring proceeds in a markedly asynchronous manner, so that the systems attain considerable diradical character, as quantified by the composition of the active-space spin-coupling pattern. The rearrangement of the electron spins from a reactant-like form to one better suited to the product takes place much later in the case of the reaction between CCl2 and ethene than in the corresponding reaction of CF2. (C) 2004 Wiley Periodicals, Inc.

    Research areas

  • cheletropic addition reactions, transition states, valence bond, spin-coupled, REACTION-PATH, SUBSTITUTED CARBENES, TRANSITION-STATES, CYCLO-ADDITIONS, TRIPLET GAPS, ETHYLENE, METHYLENE, CH2, DICHLOROCARBENE, BOND

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