MICROSOLVATION OF PARTIALLY BOUND NITRILE - $SO_{3}$ COMPLEXES

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1998

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Ohio State University

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The rotational spectrum of $HCN-HCN-SO_{3}$ and its deuterated isotopomers have been observed by pulsed nozzle Fourier transform microwave spectroscopy. The complex is a symmetric rotor with the atomic ordering indicated and preliminary analysis yields an S-N bond length of 2.43 {\AA}. This distance is approximately 0.15 {\AA} shorter than the corresponding distance in $HCN-SO_{3}$, indicating that the remote HCN has a large effect on the nitrogen - sulfur bond. This result represents the first direct probe of the effect of a nearest neighbor on the structure of a partially bonded adduct. We also present measurements of the dipole moments of $HCN-SO_{3}$ and $CH_{3}CN-SO_{3} (4.416 \pm 0.029$ D and $46.06 \pm 0.18$ D, respectively). Examination of a series of $SO_{3}$ complexes indicates a substantial increase in polarity in these systems as dative bond formation proceeds. These results will be discussed in connection with the origins of the large gas-to- solid structure changes normally observed for partially bound species.

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Author Institution: Department of Chemistry, University of Minnesota; Department of Chemistry, Carleton College, Northfield; Department of Chemistry, University of Minnesota

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