Synthesis and characterization of trimetallic cobalt, zinc and nickel complexes containing amine-bis(benzotriazole phenolate) ligands: Efficient catalysts for coupling of carbon dioxide with epoxides

New trimetallic cobalt, nickel and zinc complexes 1-3 coordinated by amine-bis(benzotriazole phenolate) ligands and ancillary acetate groups have been developed for the use of CO₂/epoxide coupling. All complexes were structurally characterized by single crystal X-ray crystallography; tri-Co complex 1 is the first solid-state example in which three different geometrical configurations exist in the same benzotriazole phenoxide metal complex. Tri-nuclear complexes 1 and 2 with cobalt and zinc metal centers were demonstrated to be very active catalysts for cycloaddition of cyclohexene oxide with CO₂ in the presence of ammonium salt co-catalysts to give cis-cyclohexene carbonate under the conditions of 80 °C and 300 psi initial CO₂ pressure. Particularly, tri-cobalt complex 1 was found to efficiently couple CO₂ with epoxides showing broad substrate scope, producing the corresponding cyclic organic carbonates with good activities and high selectivities. This is a successful example of catalysis for cyclic carbonate synthesis using one cobalt(ii) complex as a homogeneous catalyst.