Establishing the mechanism of Rh-catalysed activation of O2 by H2
Establishing the mechanism of Rh-catalysed activation of O2 by H2
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DOI：
10.1039/c1dt11599e
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发表时间：
2012-01-01
影响因子：
4
通讯作者：
Ogo, Seiji
中科院分区：
文献类型：
--
作者：
Inoki, Daisuke;Matsumoto, Takahiro;Ogo, Seiji
本文叙述了铑三联吡啶配合物在H_2O和CH_3CN中对O-_2的还原活化作用，并对其机理作了充分的阐述。铑络合物从H-2中提取电子并还原活化O-2以形成过氧活性中间体。该中间体能够将三苯基膦氧化成三苯基氧化膦。在CH 3CN中构建的模型系统提供了在H2O中的催化中间体的可分离的类似物，允许详细查看催化循环中的每个步骤。
Reductive activation of O-2 by H-2 with rhodium terpyridine complexes in H2O and CH3CN is described and the mechanism is fully elucidated. The rhodium complex extracts electrons from H-2 and reductively activates O-2 to form a peroxo active intermediate. This intermediate is able to oxidise triphenyl phosphine to triphenyl phosphine oxide. A model system constructed in CH3CN provides isolable analogues of catalytic intermediates in H2O, allowing a detailed look at each step in the catalytic cycle.