Activation of bis(trimethylsilyl) peroxide and tert-butyl hydroperoxide with oxo and peroxo complexes of vanadium, molybdenum, and tungsten for the sulfoxidation of thianthrene 5-oxide

被引:25
作者
Adam, W [1 ]
Golsch, D [1 ]
Sundermeyer, J [1 ]
Wahl, G [1 ]
机构
[1] UNIV WURZBURG,INST INORGAN CHEM,D-97074 WURZBURG,GERMANY
关键词
thianthrene; 5-oxide; peroxide; bis(trimethylsilyl); hydroperoxide; tert-butyl; oxygen transfer; peroxo complexes; catalysis; vanadium; molybdenum; tungsten;
D O I
10.1002/cber.19961291006
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Bis(trimethylsilyl) peroxide (BTSP) and tert-butyl hydroperoxide (tBuODH) were activated by various oxo and peroxo complexes of molybdenum, tungsten, and vanadium as catalysts for the sulfoxidation of thianthrene 5-oxide (SSO). A screening of a number of phosphane oxide and amine oxide ligands revealed that BTSP was most efficiently activated by the [MoO5(OPtBu(3))] complex. The best results for tBuOOH as oxygen source were achieved with the vanadates [VO(OR)(3)] (R=tBu, iPr). Comparative selectivity and rate data for the stoichiometric and catalytic sulfoxidations of SSO mediated by the MoO(5)L complex (L=OPtBu(3), OPnOct(3), ONnBu(3), ONnOct(3)) suggest that the bisperoxo metal complex is the active oxygen transfer species.
引用
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页码:1177 / 1182
页数:6
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