Flash Communication: C═O Bond Cleavage of CO 2 by a Geometrically Constrained Phosphorus-Coordinated Cobalt Complex

Treatment of dimeric complex (L1P)Co(PMe3)Cl2 (1) with CO2 (1 atm) results in the cleavage of the C═O bond in CO2, likely facilitated by the cobalt–phosphorus cooperativity, generating the CO-bridged head-to-tail dimeric complex ((L1)CoCl)2(μ-CO) (3) and compound O═P(N(o-N(2-pyridyl)(p-tBu)C6H3)2) (4). This reaction represents a rare example of cleavage of the C═O bond in CO2 enabled by late 3d metal–ligand cooperativity. Complex 3 was fully characterized by SCXRD, NMR, and elemental analysis as well as DFT calculations.