Ring strain effects on the interconversion of intermediates in the reaction of organic sulfides with singlet oxygen

被引:23
作者
Greer, A
Jensen, F
Clennan, EL
机构
[1] UNIV WYOMING,DEPT CHEM,LARAMIE,WY 82071
[2] ODENSE UNIV,DEPT CHEM,DK-5230 ODENSE M,DENMARK
关键词
D O I
10.1021/jo9600114
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Ab initio methods are used to investigate ring strain effects on sulfide-singlet oxygen reaction intermediates. The optimized persulfoxide and thiadioxirane structures derived from 3-, 4-, and 5-membered ring sulfides showed minor albeit systematic changes in geometry. These persulfoxides and thiadioxiranes are best described as distorted tetrahedral and trigonal bipyramidal in nature, respectively. We find that the persulfoxy sulfur becomes less sulfonium-ion-like in character with decreasing ring size. In addition, the persulfoxide and the thiadioxirane are nearly isoenergetic in all cases and their interconversion barriers are nearly identical. We speculate that the anticipated ring strain effect in the persulfoxide is compensated for by a weaker sulfur-oxygen interaction and the corresponding relaxation of the need to attain the energetically preferred tetrahedral geometry.
引用
收藏
页码:4107 / 4110
页数:4
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