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Structure of Triplet Propynylidene (HCCCH) as Probed by IR, UV/vis, and EPR Spectroscopy of Isotopomers

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    Structure of Triplet Propynylidene (HCCCH) as Probed by IR, UV/vis, and EPR Spectroscopy of Isotopomers
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    Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, Wisconsin 53706, and Department of Chemistry, Truman State University, Kirksville, Missouri 63501
    [email protected]
    †University of Wisconsin.
    ‡Current Address: CIMA Labs, Inc., 7325 Aspen Lane, Brooklyn Park, MN 55428.
    §Truman State University.
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2009, 131, 26, 9442–9455
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    https://doi.org/10.1021/ja901606a
    Published June 16, 2009
    Copyright © 2009 American Chemical Society
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    Abstract

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    Spectroscopic data for triplet isotopomers H−C−C−C−H, H−13C−C−C−H, and H−C−13C−C−H are consistent with computational predictions for a symmetric structure in which the terminal carbons are equivalent (C2 or C2v) and are inconsistent with a planar (Cs) structure in which they are not. Experimentally observed 13C isotope shifts in the IR spectra and 13C hyperfine coupling constants in the EPR spectra exhibit good agreement with values predicted by theory for a C2 structure. The 13C hyperfine coupling constants also provide an independent experimental estimate for the bond angles in the molecule. The isotope-dependence of the zero-field splitting parameters reveals the influence of molecular motion in modulating the values of these parameters. The interpretation of motional effects provides a basis for rationalizing the anomalously low E value, which had previously been interpreted in terms of an axially symmetric (D∞h) structure. Computational studies involving Natural Bond Orbital and Natural Resonance Theory analyses provide insight into the spin densities and the complex electronic structure of this reactive intermediate.

    Copyright © 2009 American Chemical Society

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    Supporting Information

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    Estimation of bond angles and D value in triplet HCCCH (2); EPR hyperfine simulations of triplet HCCCH (2a, 2b); UV/vis spectra of triplet HCCCH (2, 2a); experimental and computed IR spectra for triplet HCCCH (2, 2a, 2d); computed IR harmonic vibrational frequencies and intensities for triplet Cs-structures (3a, 3c); Cartesian coordinates for computed structures; complete literature citation for ref 82. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2009, 131, 26, 9442–9455
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ja901606a
    Published June 16, 2009
    Copyright © 2009 American Chemical Society
    Request reuse permissions

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