Synthesis, Characterization, and Catalytic Study of Amine-Bridged Bis(phenolato) Co(II) and Co(II/III)-M(I) Complexes (M = K or Na).

Co(II) complexes 1-3 bearing amine-bridged bis(phenolato) complexes have been synthesized through reactions of bis(phenols) with CoCl2 or Co(OAc)2. Oxidation of the Co(II) complex with air resulted in partial oxidation, generating mixed valence Co(II/III) complexes 4 and 5. In addition, due to the presence of alkali compounds (KOAc and NaOMe), 4 and 5 formed as Co-alkali metal heterometallic complexes, which are the first example of mixed valence Co(II/III)-M(I) (M = K or Na) complexes. Complexes 1-5 showed good activity in the cycloaddition of epoxides and CO2 under atmospheric pressure, generating cyclic carbonates in 40-99% yields. Co(II/III)-Na(I) complex 5 performed better in reactions of bulkier substrates, underlining the enhanced activity of mixed valence Co-alkali metal heterometallic complexes. On the contrary, complex 5 showed limited activity in copolymerization of epoxide and CO2.