Abstract
The molecular structure and benzene ring distortions of ethynylbenzene have been investigated by gas-phase electron diffraction and ab initio MO calculations at the HF/6-31G* and 6-3G** levels. Least-squares refinement of a model withC 2v, symmetry, with constraints from the MO calculations, yielded the following important bond distances and angles:r g(C i -C o )=1.407±0.003 Å,r g(C o -C m )=1.397±0.003 Å,r g(C m -C p )=1.400±0.003 Å,r g(Cr i -CCH)=1.436 ±0.004 Å,r g(C=C)=1.205±0.005 Å, ∠C o -C i -C o =119.8±0.4°. The deformation of the benzene ring of ethynylbenzene given by the MO calculations, including <Co-Ci-Co=119.4°, is insensitive to the basis set used and agrees with that obtained by low-temperature X-ray crystallography for the phenylethynyl fragment, C6H5-C≡C-, in two different crystal environments. The partial substitution structure of ethynylbenzene from microwave spectroscopy is shown to be inaccurate in the ipso region of the benzene ring.
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Schultz, G., Nagy, T., Portalone, G. et al. Molecular structure of ethynylbenzene from electron diffraction and ab initio molecular orbital calculations. Struct Chem 4, 183–190 (1993). https://doi.org/10.1007/BF00679344
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DOI: https://doi.org/10.1007/BF00679344