Trialkylborane-Assisted CO(2) Reduction by Late Transition Metal Hydrides.
Trialkylborane-Assisted CO(2) Reduction by Late Transition Metal Hydrides.
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三烷基硼烷辅助后过渡金属氢化物还原 CO(2)。
DOI：
10.1021/om200364w
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发表时间：
2011
期刊：
影响因子：
2.8
通讯作者：
Bercaw,JohnE
中科院分区：
文献类型：
--
作者：
Miller,AlexanderJM;Labinger,JayA;Bercaw,JohnE
三烷基硼烷添加剂促进双（二膦）Ni（II）和Rh（III）氢化物络合物将CO2还原为甲酸盐。可以由二氢形成的后过渡金属氢化物将氢化物转移到CO2，得到甲酸酯-硼烷加合物。硼烷必须具有适当的刘易斯酸性：较弱的酸不显示显著的氢化物转移增强，而较强的酸在没有CO2还原的情况下提取氢化物。该机制可能涉及预平衡氢化物转移，然后形成稳定的甲酸酯-硼烷加合物。
Trialkylborane additives promote reduction of CO2to 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 CO2to 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 CO2reduction. The mechanism likely involves a pre-equilibrium hydride transfer followed by formation of a stabilizing formate–borane adduct.