Fundamental lessons in carbon fixation chemistry: Molybdenum-mediated reduction of C_1 oxygenates

Abstract

The controlled redn. of CO_2 and CO to C≥2 products is crit. for the synthesis of clean fuels, but these multi-electron reactions are challenging to control and mechanistically poorly understood. A series of Mo complexes, bearing a terphenyl diphosphine ligand scaffold, shed light on important mechanistic aspects of CO_2 redn., CO deoxygenation, and CO reductive catenation. A rare example of a terminal Mo carbide complex acts as a precursor to downstream C-C coupling chemistries. Low temp. synthesis and spectroscopy, kinetics, and isotopic labeling provide key insights into design elements that promote advantageous reactivity, while mapping out the elementary steps by which C_1 oxygenates are reduced and coupled at a single metal site.

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