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Metal-mediated activation of carbon dioxide in the gas phase: Mechanistic insight derived from a combined experimental/computational approach

机译:金属介导的气相中二氧化碳的活化:从综合的实验/计算方法获得的机理见解

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In this invited review we address, from a mechanistic point of view, three fundamental reactions of carbon dioxide transformation in the gas phase: (i) its reduction to carbon monoxide via oxygen-atom transfer to a suitable oxygen acceptor, (ii) translocation of a hydride from metal hydrides to generate a formate ligand, and (iii) coupling processes with CO2 to make C-C and C-O bonds. Where appropriate, the findings are compared with related reactions in the condensed phase. The gas-phase studies described, in conjunction with computational work, permit to uncover numerous mechanistic aspects of elementary steps in the making and breaking of bonds, reactions which, by definition, are obscured in solution due to ill-defined effects of the environment. (C) 2016 Elsevier B.V. All rights reserved.
机译:在本受邀的综述中,我们从机理的角度探讨了气相中二氧化碳转化的三个基本反应:(i)通过将氧原子转移至合适的氧受体将其还原为一氧化碳,(ii)由金属氢化物生成氢化物以生成甲酸配体,以及(iii)与CO2偶联的过程以形成CC和CO键。在适当的情况下,将结果与浓缩阶段的相关反应进行比较。所描述的气相研究与计算工作相结合,可以揭示形成和破坏键的基本步骤的许多机械方面,根据定义,由于环境的不确定性,反应在解决方案中被掩盖。 (C)2016 Elsevier B.V.保留所有权利。

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