【摘 要】
：
Density functional theory(DFT)calculations were used to study the mechanisms for hydrogenation of carbon dioxide catalyzed by the tetraphos-ligated(PP3: P(CH2CH2PPh2)3)cobalt complexes.The monohydride
【机 构】
：
Guangzhou Institute of Energy Conversion,Chinese Academy of Sciences
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Density functional theory(DFT)calculations were used to study the mechanisms for hydrogenation of carbon dioxide catalyzed by the tetraphos-ligated(PP3: P(CH2CH2PPh2)3)cobalt complexes.The monohydride catalytic pathway(Path Ⅰ)and the dihydride catalytic pathway(Path Ⅱ)for the hydrogenation of CO2 have been explored,respectively.The largest free energy barrier in Path Ⅱ is 19.1 kcal mol-1 significantly lower than that of 22.8 kcal mol-1 in Path Ⅰ,corresponding to the hydride transfer from cobalt center to CO2.The detailed comparisons of the possible pathways suggest that the Path Ⅱ is much more favored than Path Ⅰ and that it is not necessary to form the monohydride species in the whole catalytic cycles.Our results unambiguously demonstrate that the active catalyst is the dihydride rather than the monohydride,which are consistent with the experimental observations,most importantly,and provide a detailed mechanistic insight.
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