Carbon dioxide fixation: bifunctional complexes containing acidic and basic sites working as reversible carriers

Abstract

Carbon dioxide fixation in its intact form is achieved from ''bifunctional'' complexes containing in their structure a nucleophilic cobalt(I) and an alkali cation: Co(R-salen)M (R-salen = substituted salen ligand; salen = N,N'-ethylenebis(salicylideneaminato); M = Li, Na, K, Cs). The fixation of CO/sub 2/ by such systems displays different degrees of reversibility depending on the reaction solvent and the nature of the alkali cation. The X-ray analysis carried out on (Co(n-Pr-salen)K-(CO)/sub 2/(THF)) shows carbon dioxide anchored to the cobalt through a Co-C sigma bond, while the oxygens interact with the alkali cation, in a polymeric structure. IR spectra are diagnostic for the presence of CO/sub 2/ bonded as a bent molecule in a reduced form displaying three strong bands in the following ranges: 1700-1650, 1300-1250, and 1250-1200 cm/sup -1/. The binding of CO/sub 2/ is partially prevented in the presence of a crown ether, which can complex the alkali cation. The reaction of (Co(salen)Na(CO/sub 2/)) and (Co(salen)Na(THF)) with dicyclohexano-18 crown-6(DCHC) gave a complex, (Co(salen)Na)/sub 2/(DCHC), whose structure shows the presence of the intact bifunctional unit where, however, all the coordination sites around the alkali cation are filled by the oxygens from salen and DCHC and are not further available for bindingmore » the oxygen atoms of the CO/sub 2/ molecule. Crystallographic details and the final R factor for specific observed reflections are given for (Co(n-Pr-salen)K(CO/sub 2/)(THF))/sub n/, (CO(n-Pr-salen)K(CO/sub 2/)(THF))/sub n/, (Co(salen)Na)/sub 2/(DCHC).« less