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Direct Detection of a Triplet Vinylnitrene, 1,4-Naphthoquinone-2-ylnitrene, in Solution and Cryogenic Matrices

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    Direct Detection of a Triplet Vinylnitrene, 1,4-Naphthoquinone-2-ylnitrene, in Solution and Cryogenic Matrices
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    † Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, United States
    ‡ Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan
    § School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, Queensland 4072, Australia
    [email protected]
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2015, 137, 12, 4207–4214
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    https://doi.org/10.1021/jacs.5b00998
    Published March 11, 2015
    Copyright © 2015 American Chemical Society
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    Abstract

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    The photolysis of 2-azido-1,4-naphthoquinone (1) in argon matrices at 8 K results in the corresponding triplet vinylnitrene 32, which was detected directly by IR spectroscopy. Vinylnitrene 32 is stable in argon matrices but forms 2-cyanoindane-1,3-dione (3) upon further irradiation. Similarly, the irradiation of azide 1 in 2-methyltetrahydrofuran (MTHF) matrices at 5 K resulted in the ESR spectrum of vinylnitrene 32, which is stable up to at least 100 K. The zero-field splitting parameters for nitrene 32, D/hc = 0.7292 cm–1 and E/hc = 0.0048 cm–1, verify that it has significant 1,3-biradical character. Vinylnitrene 32 (λmax ∼ 460 nm, τ = 22 μs) is also observed directly in solution at ambient temperature with laser flash photolysis of 1. Density functional theory (DFT) calculations support the characterization of vinylnitrene 32 and the proposed mechanism for its formation. Because vinylnitrene 32 is relatively stable, it has potential use as a building-block for high-spin assemblies.

    Copyright © 2015 American Chemical Society

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    Supporting Information

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    1H NMR and IR spectra of 1; graph showing the correlation of D with the natural spin densities ρ for several nitrenes; Cartesian coordinates and energies of 1–5; difference IR spectra in Ar matrices. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cite this: J. Am. Chem. Soc. 2015, 137, 12, 4207–4214
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.5b00998
    Published March 11, 2015
    Copyright © 2015 American Chemical Society
    Request reuse permissions

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