Exploring two-state reactivity pathways in the cycloaddition reactions of triplet methylene

Patricia Pérez, J. Andrés, V. S. Safont, Renato Contreras, O. Tapia

Resultado de la investigación: Contribución a una revistaArtículo

11 Citas (Scopus)

Resumen

Spin forbidden 1,2-cycloadditions of triplet methylene to alkenes have been theoretically studied as an example of the two-state reactivity paradigm in organic chemistry. The cycloadditions of triplet methylene to ethylene and the (E)- and (Z)-2-butene isomers show spin inversion after the transition state and therefore with no effect on the reaction rate. A local analysis shows that while triplet methylene addition to alkenes leading to the formation of a biradical intermediate is driven by spin polarization, the ring closure step to yield cyclopropane is a pericyclic process. We have found that at the regions in the potential energy surface where the spin crossover is likely to occur, the spin potential in the direction of increasing spin multiplicity, μs +, tends to equalize the one in the direction of decreasing spin multiplicity, μ̄S This equalization facilitates the spin transfer process driven by changes in the spin density of the system.

Idioma originalInglés
Páginas (desde-hasta)4178-4184
Número de páginas7
PublicaciónJournal of Physical Chemistry A
Volumen109
N.º18
DOI
EstadoPublicada - 12 may 2005

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  • Química física y teórica

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