Conversion of carbon oxygenates into higher value compounds is a key component to carbon-neutral fuel synthesis and carbon fixation strategies. Approaches include CO₂ reduction to formate or CO as well as downstream Fischer-Tropsch reactions wherein CO reduction and C-C bond formation afford hydrocarbon products. In biological and heterogeneous systems, such multi-electron and -proton transformations occur at polynuclear metal active sites isolated within protein matrix or on the catalyst surface. Discrete molecular species provide a unique opportunity to interrogate mechanistic questions while leveraging the wealth of readily available solution spectroscopic methods. To that end, the discussion focuses on our current efforts to effect conversions of carbon oxygenates, including our ongoing work on factors that control CO₂ insertion into multimetallic hydride complexes, and C–C bond reactions involving CO₂ and CO.