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Photolysis of (3-Methyl-2H-azirin-2-yl)-phenylmethanone: Direct Detection of a Triplet Vinylnitrene Intermediate

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    Photolysis of (3-Methyl-2H-azirin-2-yl)-phenylmethanone: Direct Detection of a Triplet Vinylnitrene Intermediate
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    † Department of Chemistry, University of Cincinnati, Ohio 45221-0172, United States
    ‡ Department of Chemistry, University of Victoria, Victoria, BC, Canada
    § Division of Space Life Science, Universities Space Research Association, Houston, Texas 77058, United States
    E-mail: [email protected]
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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2011, 76, 24, 9934–9945
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    https://doi.org/10.1021/jo200877k
    Published July 6, 2011
    Copyright © 2011 American Chemical Society
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    Abstract

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    The photoreactivity of (3-methyl-2H-azirin-2-yl)-phenylmethanone, 1, is wavelength-dependent (Singh et al. J. Am. Chem. Soc. 1972, 94, 1199−1206). Irradiation at short wavelengths yields 2P, whereas longer wavelengths produce 3P. Laser flash photolysis of 1 in acetonitrile using a 355 nm laser forms its triplet ketone (T1K, broad absorption with λmax ∼ 390–410 nm, τ ∼ 90 ns), which cleaves and yields triplet vinylnitrene 3 (broad absorption with λmax ∼ 380–400 nm, τ = 2 μs). Calculations (B3LYP/6-31+G(d)) reveal that T1K of 1 is located 67 kcal/mol above its ground state (S0) and has a long C–N bond (1.58 Å), and the calculated transition state to form 3 is only 1 kcal/mol higher in energy than T1K of 1. The calculations show that 3 has significant 1,3-carbon iminyl biradical character, which explains why 3 reacts efficiently with oxygen and decays by intersystem crossing to the singlet surface. Photolysis of 1 in argon matrixes at 14 K produced ketene imine 7, which presumably is formed from 3 intersystem crossing to 7. In comparison, photolysis of 1 in methanol with a 266 nm laser produces mainly ylide 2 (λmax ∼ 380 nm, τ ∼ 6 μs, acetonitrile), which decays to form 2P. Ylide 2 is formed via singlet reactivity of 1, and calculations show that the first singlet excited state of the azirine chromophore (S1A) is located 113 kcal/mol above its S0 and that the singlet excited state of the ketone (S1K) is 85 kcal/mol. Furthermore, the transition state for cleaving the C–C bond in 1 to form 2 is located 49 kcal/mol above the S0 of 1. Thus, we theorize that internal conversion of S1A to a vibrationally hot S0 of 1 forms 2, whereas intersystem crossing from S1K to T1K results in 3.

    Copyright © 2011 American Chemical Society

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    Cartesian coordinates, energies, and vibrational frequencies. This material is available free of charge via the Internet at http://pubs.acs.org.

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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2011, 76, 24, 9934–9945
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jo200877k
    Published July 6, 2011
    Copyright © 2011 American Chemical Society
    Request reuse permissions

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