后过渡金属氢化物在三烷基硼烷辅助下对二氧化碳的还原反应
Trialkylborane-Assisted CO(2) Reduction by Late Transition Metal Hydrides.
作者信息
Miller Alexander J M, Labinger Jay A, Bercaw John E
机构信息
Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125.
出版信息
Organometallics. 2011;30(16):4308-4314. doi: 10.1021/om200364w.
Abstract
Trialkylborane additives promote reduction of CO(2) to formate by bis(diphosphine) Ni(II) and Rh(III) hydride complexes. The late transition metal hydrides, which can be formed from dihydrogen, transfer hydride to CO(2) to give a formate-borane adduct. The borane must be of appropriate Lewis acidity: weaker acids do not show significant hydride transfer enhancement, while stronger acids abstract hydride without CO(2) reduction. The mechanism likely involves a pre-equilibrium hydride transfer followed by formation of a stabilizing formate-borane adduct.
摘要
三烷基硼烷添加剂可促进双（二膦）镍（II）和铑（III）氢化物配合物将二氧化碳还原为甲酸盐。这些可由氢气形成的后过渡金属氢化物将氢化物转移至二氧化碳，生成甲酸盐-硼烷加合物。硼烷必须具有适当的路易斯酸度：酸性较弱的硼烷不会显著增强氢化物转移，而酸性较强的硼烷会夺取氢化物而不发生二氧化碳还原。其机理可能涉及氢化物转移的预平衡，随后形成稳定的甲酸盐-硼烷加合物。
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