Reactivity and Intersystem Crossing of Singlet Methylene in Solution

Nicholas J. Turro, Yuan Cha, Ian R. Gould

Research output: Contribution to journalArticle

43 Scopus citations

Abstract

Evidence is reported which demonstrates that singlet methylene, produced from the photolysis of diazomethane or diazirine, undergoes intersystem crossing to form triplet methylene in perfluorohexane solvent. The results of triplet sensitized photolysis and of direct photolysis experiments with dilute concentrations of substrate (cis- and trans-2-pentene and chloroform) appear to be essentially identical. Stern-Volmer analyses of the competition kinetics between acetonitrile and 2-pentenes or chloroform for singlet methylene are consistent with the near diffusion controlled reactivity of singlet methylene. With the assumption of diffusion-controlled reactions for singlet methylene, plots of the quantum yield for singlet vs. triplet reaction for methylene allow the first estimate (<8 × 108 s-1) of the rate of intersystem crossing of singlet methylene in the condensed phase. This value is considerably smaller than the value that is extrapolated to the solution phase from results in the gas phase. The possible reasons for this difference are discussed.

Original languageEnglish (US)
Pages (from-to)2101-2107
Number of pages7
JournalJournal of the American Chemical Society
Volume109
Issue number7
DOIs
StatePublished - Apr 1 1987
Externally publishedYes

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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