Chromium Diamino-bis(phenolate) Complexes as Catalysts for the Ring-Opening Copolymerization of Cyclohexene Oxide and Carbon Dioxide.

Chromium diamino-bis(phenolate) complexes, CrXL [where L = 6,6'-((1,4-diazepane-1,4-diyl)bis(methylene))bis(2,4-dimethylphenolato) and X = Cl- (1), OH- (2), and N3- (3)], were prepared and characterized by MALDI-TOF MS and single-crystal X-ray diffraction. Complex 1 crystallized as two linkage isomers, specifically a green chloride-bridged dimer (1) and a pink asymmetrically bridged isomer exhibiting one chloride bridging atom and one bridging phenolate oxygen (1'). Adventitious moisture during sample handling causes the formation of hydroxide-containing complex 2. The reaction of 1 with PPNN3 (where PPN = bis(triphenylphosphine)iminium) permits the isolation of a crystalline chromium azide complex, 3, which was structurally authenticated. Complex 1 showed good activity toward the ring-opening copolymerization of cyclohexene oxide and carbon dioxide with an added chloride, azide, or 4-(dimethylamino)pyridine (DMAP) cocatalyst to give a completely alternating polycarbonate with a narrow molecular weight dispersity.