Sulfur inversion in and molecular structure of meso-3,4-diethyl-3,4-dimethyl-1-phenylthiolanium tetrafluoroborate.

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概要

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• Kinetics of sulfur inversion in the title compound was studied by the classical method to afford the following kinetic parameters for the process (1<I>r</I>,3<I>R</I>,4<I>S</I>)→(1<I>s</I>,3<I>R</I>,4<I>S</I>): Δ<I>H</I><SUP>\neweq</SUP> 25.7±0.3 kcal mol<SUP>−1</SUP>, Δ<I>S</I><SUP>\neweq</SUP> −2.2±0.8 cal mol<SUP>−1</SUP> K<SUP>−1</SUP>. X-Ray crystallography of one isomer (1<I>r</I>,3<I>R</I>,4<I>S</I>) in which the methyl groups are cis to the phenyl group shows some abnormal bond lengths and conformations due to the steric congestion in the 3,4-region of the thiolane ring. The anomalies in the structure are pointed out by comparing the structure with those closely related and the correlation of them with the barrier height to inversion is discussed.

• 公益社団法人 日本化学会の論文

著者

• Oki Michinori

  Department Of Chemistry Faculty Of Science Okawama University Of Science

• Yamada Yasuhisa

  Department of Chemistry, Faculty of Science, The University of Tokyo

• Murata Shigeru

  Institute for Molecular Science

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