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: Article

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

Huella dactilar

Cycloaddition
cycloaddition
Alkenes
methylene
reactivity
Potential energy surfaces
Spin polarization
Isomers
Reaction rates
alkenes
Direction compound
organic chemistry
cyclopropane
butenes
closures
crossovers
reaction kinetics
ethylene
isomers
potential energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Citar esto

Pérez, Patricia ; Andrés, J. ; Safont, V. S. ; Contreras, Renato ; Tapia, O. / Exploring two-state reactivity pathways in the cycloaddition reactions of triplet methylene. En: Journal of Physical Chemistry A. 2005 ; Vol. 109, N.º 18. pp. 4178-4184.
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abstract = "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.",
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Exploring two-state reactivity pathways in the cycloaddition reactions of triplet methylene. / Pérez, Patricia; Andrés, J.; Safont, V. S.; Contreras, Renato; Tapia, O.

En: Journal of Physical Chemistry A, Vol. 109, N.º 18, 12.05.2005, p. 4178-4184.

Resultado de la investigación: Article

TY - JOUR

T1 - Exploring two-state reactivity pathways in the cycloaddition reactions of triplet methylene

AU - Pérez, Patricia

AU - Andrés, J.

AU - Safont, V. S.

AU - Contreras, Renato

AU - Tapia, O.

PY - 2005/5/12

Y1 - 2005/5/12

N2 - 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.

AB - 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.

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