Olefin rearrangement resulting from the gas-phase KrF laser photolysis of Cr(CO)6

William Tumas, Barbara Gitlin, Alan M. Rosan, James T. Yardley

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Abstract

We have found that irradiation of Cr(CO)6-1-butene mixtures in the gas phase with a KrF laser (248 nm) results in the efficient (yield ∼0.2) isomerization of 1-butene to 2-butene, in marked contrast to results in solution. The primary photochemical yield is independent of 1-butene pressure and of Cr(CO)6 pressure over wide pressure ranges. Secondary photochemical processes are also found, the importance of which depends upon 1-butene pressure. We also report yields of species Cr(CO)m(PF3)6-m resulting from irradiation of Cr(CO)6-PF3 mixtures at 248 nm. At high dilution [Cr(CO)6:PF3 = 2 × 10-3], we find relative yields of 0.10, 0.14, 0.73, and 0.03 for Cr(CO)2(PF3)4, Cr(CO)3(PF3)3, Cr(CO)4(PF3)2, and Cr(CO)5PF3, respectively. These results suggest a high degree of fragmentation following optical excitation at 248 nm. We present a reasonable kinetic model to explain the observed isomerization of butene in which a primary photofragment, probably Cr(CO)3 or Cr(CO)2, is the active species.

Original languageEnglish
Pages (from-to)55-59
Number of pages5
JournalJournal of the American Chemical Society
Volume104
Issue number1
Publication statusPublished - 1982

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Photolysis
Alkenes
Carbon Monoxide
Butenes
Olefins
Lasers
Gases
Isomerization
Irradiation
Pressure
Photoexcitation
Dilution
Photochemical Processes
Kinetics

ASJC Scopus subject areas

  • Chemistry(all)

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Olefin rearrangement resulting from the gas-phase KrF laser photolysis of Cr(CO)6 . / Tumas, William; Gitlin, Barbara; Rosan, Alan M.; Yardley, James T.

In: Journal of the American Chemical Society, Vol. 104, No. 1, 1982, p. 55-59.

Research output: Contribution to journalArticle

Tumas, William ; Gitlin, Barbara ; Rosan, Alan M. ; Yardley, James T. / Olefin rearrangement resulting from the gas-phase KrF laser photolysis of Cr(CO)6 . In: Journal of the American Chemical Society. 1982 ; Vol. 104, No. 1. pp. 55-59.
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