Electrocatalysts for the reduction of CO2 are of interest in the production of solar fuels, and as a means of mitigating atmospheric CO2. Stopped-flow mixing in tandem with rapid scan IR spectroscopy will be described as a technique for studying the kinetics and mechanistic properties of reactions of catalytically relevant [Re(bpy-tBu)(CO)3]�1 and [Re(bpy)(CO)3]�1 species with CO2. [Re(bpy-tBu)(CO)3]�1 is shown to react ten times faster than [Re(bpy)(CO)3]�1 with CO2. Both reactions appear to proceed by a direct two-electron oxidative addition of CO2 to the Re center. The electrocatalytic properties, X-ray crystallographic studies, and infrared spectroelectrochemistry (IR-SEC) of earth-abundant Mn(bpy-tBu)(CO)3X catalysts for the reduction of CO2 to CO will be discussed. Unlike the analogous Re system, these catalysts require the addition of Br�nsted acids for catalyst turnover. The Mn catalysts reduce CO2 to CO at lower overpotentials and have similar catalytic activity when compared to their Re counterparts.

Carbon dioxide reduction by rhenium and manganese bipyridyl complexes: Kinetic and mechanistic studies

245th National Meeting (2013)

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