Concerning the denticity of the dimethylsulfinyl anion in Meisenheimer complexation

被引:15
作者
Buncel, E [1 ]
Park, KT
Dust, JM
Manderville, RA
机构
[1] Queens Univ, Dept Chem, Kingston, ON K7L 3N6, Canada
[2] Korea Natl Univ Educ, Dept Chem Educ, Chungbuk 363791, South Korea
[3] Sir Wilfred Grenfell Coll, Dept Chem & Environm Sci, Corner Brook, NF A2H 6P9, Canada
[4] Wake Forest Univ, Dept Chem, Winston Salem, NC 27109 USA
关键词
D O I
10.1021/ja0298489
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The denticity (O, S-, and C-nucleophilic reactivity) of the dimethylsulfinyl carbanion ("dimsyl") toward 1,3,5-trinitrobenzene (TNB) has been studied by NMR spectroscopy, and structures of adducts have been assigned. Three dimsyl adducts are observed for the first time and have been ascribed to the O-adduct 15, the S-adduct 16, and the C-adduct 17. The kinetic (15 > 16 > 17) and thermodynamic preference (17 > 16 > 15) for the reactivity of dimsyl toward TNB is compared to the known O- and C-reactivity of enolate anions and the O- and S-reactivity of dimethyl sulfoxide. Thus, dimsyl apparently represents a unique system in which three adjacent atoms having unshared electron pairs can utilize these in covalent bond formation.
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页码:5388 / 5392
页数:5
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