The reduction of CO2 by non-precious metals poses an interesting challenge in synthetic chemistry. A low coordinate Co(I) complex reduces CO2 to form a Co(I) monocarbonyl species and a bridging carbonate species. NMR solution susceptibility studies reveal the monocarbonyl species to be three coordinate, S = 1. Solid state characterization and geometry optimized DFT calculations suggest a spin state change to S = 0 upon crystallization by adoption of a pseudo square-planar geometry. The bridging carbonate and monocarbonyl species exhibit rapid isomerization in solution. Formation of the bridging carbonate species from the reaction of CO2 with an independently synthesized bridging oxo complex of Co(II) suggests the formation of an oxo intermediate upon CO2 reduction.

Reduction of CO<sub>2</sub> using a masked two-coordinate Co(I) complex

246th National Meeting (2013)

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Reduction of CO2 using a masked two-coordinate Co(I) complex

Reduction of CO₂ using a masked two-coordinate Co(I) complex