Rhodium-Mediated Oxygenation of Nitriles with Dioxygen: Isolation of Rhodium Derivatives of Peroxyimidic Acids.
Rhodium-Mediated Oxygenation of Nitriles with Dioxygen: Isolation of Rhodium Derivatives of Peroxyimidic Acids.
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DOI：
10.1002/chem.201502481
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发表时间：
2015-08
期刊：
影响因子：
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通讯作者：
Annemarie Bittner;T. Braun;R. Herrmann;S. Mebs
中科院分区：
文献类型：
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作者：
Annemarie Bittner;T. Braun;R. Herrmann;S. Mebs
在铑介导的腈转化为酰胺的反应中，氧气被用作氧化剂。中间物种和模型化合物的表征以及同位素标记研究提供了对反应机理的深入了解。铑与腈的过氧化氢或过氧化甲基络合物转化为金属环铑-κ（2）-（N，O）-过氧亚胺化合物是必不可少的关键步骤。前者可从铑（III）过氧化物络合物获得，后者代表Payne试剂（过氧亚胺酸）的铑衍生物。
Dioxygen is used as the oxygenation agent in the rhodium-mediated conversion of nitriles into amides. The characterization of intermediate species and model compounds as well as isotope-labeling studies provided an insight into the reaction mechanism. The conversions of rhodium hydroperoxido or methylperoxido complexes with nitriles into metallacyclic rhodium-κ(2)-(N,O)-peroxyimidate compounds represent essential key steps. The former are accessible from a rhodium(III) peroxido complex and the latter represent rhodium derivatives of Payne's reagent (peroxyimidic acids).