Department of Inorganic Chemistry, Indian Association for the Cultivation of Science , Kolkata 700032, India.
J Am Chem Soc. 2015 Sep 9;137(35):11214-7. doi: 10.1021/jacs.5b05992. Epub 2015 Aug 27.
The reduction of CO2 by an iron porphyrin complex with a hydrogen bonding distal pocket involves at least two intermediates. The resonance Raman data of intermediate I, which could only be stabilized at -95 °C, indicates that it is a Fe(II)-CO2(2-) adduct and is followed by an another intermediate II at -80 °C where the bound CO2 in intermediate I is protonated to form a Fe(II)-COOH species. While the initial protonation can be achieved using weak proton sources like MeOH and PhOH, the facile heterolytic cleavage of the C-OH bond in intermediate II requires strong acids.
一种带有氢键远端口袋的铁卟啉配合物还原 CO2 至少涉及两种中间体。在-95°C 下只能稳定存在的中间体 I 的共振拉曼数据表明，它是一个 Fe(II)-CO2(2-)加合物，随后在-80°C 下形成另一个中间体 II，其中中间体 I 中的结合 CO2 被质子化形成 Fe(II)-COOH 物种。虽然初始质子化可以使用甲醇和苯酚等弱质子源来实现，但中间体 II 中 C-OH 键的易发生均裂需要强酸。
