Mechanism of selective oxidation of organic sulfides with oxo(salen)chromium(V) complexes

被引：88
作者：
Sevvel, R
Rajagopal, S [1 ]
Srinivasan, C
Alhaji, NI
Chellamani, A
机构：
[1] Madurai Kamaraj Univ, Dept Mat Sci, Madurai 625021, Tamil Nadu, India
[2] Madurai Kamaraj Univ, Sch Chem, Madurai 625021, Tamil Nadu, India
[3] Manonmanian Sundaranar Univ, Dept Chem, Tirunelveli 627012, India
来源：
JOURNAL OF ORGANIC CHEMISTRY | 2000年 / 65卷 / 11期
关键词：
D O I：
10.1021/jo9916380
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The selective oxidation of organic sulfides to sulfoxides by oxo(salen)chromium(V) complexes in acetonitrile is overall second-order, first-order each in the oxidant and the substrate. The rate constant, k(2), values of several para-substituted phenyl methyl sulfides correlate linearly with Hammett sigma constants and the rho values are in the range of -1.3 to -2.7 with different substituted oxo(salen)chromium(v) complexes. The reactivity of different alkyl sulfides is in accordance with Taft's steric substituent constant, E-s. A mechanism involving direct oxygen atom transfer from the oxidant to the substrate rather than electron transfer is envisaged. Correlation analyses show the presence of an inverse relationship between reactivity and selectivity in the reaction of various sulfides with a given oxo(salen)chromium(v) complex and vice versa. Mathematical treatment of the results shows that this redox system falls under strong reactivity-selectivity principle (RSP).
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收藏
页码：3334 / 3340
页数：7
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