Acta Phys. -Chim. Sin. ›› 1993, Vol. 9 ›› Issue (03): 402-405.doi: 10.3866/PKU.WHXB19930321

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Structures of α-Chloromethylsulfide Radical and its Captodative Effect

Li Wei-Xing; Zhou Xun-Jun; Cai Guo-Qiang   

  1. Department of Chemical Engineering, Zhejiang Institute of Technology, Hangzhou 310014; Department of Chemistry, Hangzhou University, Hangzhou 310028; Department of Chemistry, Zhejiang University, Hangzhou 310027
  • Received:1991-12-18 Revised:1992-04-05 Published:1993-06-15
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Abstract: α-chlorosulfide is one of the important organosulfur compounds. In this article, the structural parameters of α-chloromethylsulfide and its free radical are calculated by ab initio method at STO-3G and 4-31G levels. The Cl-C-S-C dihedral angles of the most stable structures both for the molecule and the free radical are about 60°. However the bond length of C—S bond and C—Cl bond in free radical are shorter than those in molecule. The △E_(cd)~K and △E_(cd)~T are -4.08 and -2.44 kJ·mol~(-1) respectively, it meansec that the electron-donating group, SCH_3, and electron-withdrawing group, Cl, lead to a minute extra stabilization, when they are bearing on the same carbon atom.

Key words: Free radical, α-chloromethylsulfide, Captodative effect