Our group has recently reported a monometallic Molybdenum complex supported by a terphenyl diphosphine ligand capable of undergoing multielectron reductive processes. Various oxidation states of the metal center are stabilized by the ability of the ligand to accommodate different binding modes. For example, the arene π-system displays η2, η4, η6 binding while one of the phosphine arms reversibly dissociates. To further study the significance of the hemilability of the ligand donor arms, a monometallic Mo dicarbonyl complex supported by an asymmetric terphenyl phosphine-phenol ligand (POH) framework has been isolated. Deprotonation and treatment of the (PMo(CO)2OH) complex with KC8 or K(C10H8) yields a reduced Mo species. Subsequent treatment of the reduced species with a silyl electrophile effected a two-electron reductive C-C coupling of the carbonyl moieties. Mechanism of the reaction and ligand effects will be discussed. This work could provide insights for the conversion of C1 feedstock to value-added products.

Selective two-electron reduction of carbon monoxide mediated by molybdenum complexes supported on an asymmetric phenol phosphine ligand

251st National Meeting (2016)

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