碘化四-(4-三甲胺苯基)卟啉合钴与含氮有机碱的轴向配位反应

THE AXIAL REACTION OF COBALT(Ⅱ)TETRAKIS(4-TRIMETHYL AMINO PHENYL)-PORPHYRIN IODIDE HYDRATE WITH ORGANIC BASES

碘化四-(4-三甲胺苯基)卟啉合钴(简写Co(Ⅱ)TMAPPI)是较好的CO_2电化学还原反应的催化剂。有咪唑存在时此反应的电流效率和CO产量明显提高,吡啶则否。本文报道Co(Ⅱ)TMAPPI与不同类型含氮有机碱的轴向配位反应研究,以进一步阐明CO_2电催化还原反应机理及有机碱(如咪唑)的助催化作用。

The equilibrium constants and coordination numbers for axial reaction of cobalt(Ⅱ)tetrakis (4-trimethylamino phenyl) - porphyrin iodide hydrate (abb. Co(Ⅱ) TMAPPI) withnitrogen containing organic bases were measured by spectral technique. The results showthat Co(Ⅱ)TMAPPI forms 1:2 adducts with imidazoline (Im) and benzimidazoline (PhIm),but 1: 1 adducts with pyridine(Py) and n-propylaniline (P_1NH_2). The mechanism of the auxi-liary catalytic effect of nitrogen containing organic bases on the electrocatalytic reductionof CO_2 with Co(Ⅱ)TMAPPI was discussed.