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

Treatment of dimeric complex [(L1P)Co(PMe3)Cl]2 (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.