Flash Communication: Ligand Centered Cooperative O–H Bond Splitting by a Mo(CO)5(phosphine) Complex

The synthesis and reactivity of a molybdenum carbonyl complex ligated by geometrically constrained phosphorus trisamide are reported. Reaction with potassium tert -butoxide or methanol triggers ligand-centered substrate activation, leading to planarization of the phosphine donor ligand. P–O bond formation, decarbonylation, and insertion of the molybdenum center into a ligand P–N bond result in the formation of molybdenum tetracarbonyl complexes ligated by rigid N,P-chelate ligands.