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Fixation and chemical reduction of CO 2 are important for utilization of this abundant resource, and understanding the detailed mechanism of C-O cleavage is needed for rational development of CO 2 reduction methods. Here, we describe a detailed analysis of the mechanism of the reaction of a masked two-coordinate cobalt(i) complex, L  t Bu Co (where L  t Bu = 2,2,6,6-tetramethyl-3,5-bis[(2,6-diisopropylphenyl)imino]hept-4-yl), with CO 2 , which yields two products of C-O cleavage, the cobalt(i) monocarbonyl complex L  t Bu Co(CO) and the dicobalt(ii) carbonate complex (L  t Bu Co) 2 (μ-CO 3 ). Kinetic studies and computations show that the κ N ,η 6 -arene isomer of L  t Bu Co rearranges to the κ 2  N , N' binding mode prior to binding of CO 2 , which contrasts with the mechanism of binding of other substrates to L  t Bu Co. Density functional theory (DFT) studies show that the only low-energy pathways for cleavage of CO 2 proceed through bimetallic mechanisms, and DFT and highly correlated domain-based local pair natural orbital coupled cluster (DLPNO-CCSD(T)) calculations reveal the cooperative effects of the two metal centers during facile C-O bond rupture. A plausible intermediate in the reaction of CO 2 with L  t Bu Co is the oxodicobalt(ii) complex L  t Bu CoOCoL  t Bu , which has been independently synthesized through the reaction of L  t Bu Co with N 2 O. The rapid reaction of L  t Bu CoOCoL  t Bu with CO 2 to form the carbonate product indicates that the oxo species is kinetically competent to be an intermediate during CO 2 cleavage by L  t Bu Co. L  t Bu CoOCoL  t Bu is a novel example of a thoroughly characterized molecular cobalt-oxo complex where the cobalt ions are clearly in the +2 oxidation state. Its nucleophilic reactivity is a consequence of high charge localization on the μ-oxo ligand between two antiferromagnetically coupled high-spin cobalt(ii) centers, as characterized by DFT and multireference complete active space self-consistent field (CASSCF) calculations.

chemical science

Reduction of CO<sub>2</sub> by a masked two-coordinate cobalt(<scp>i</scp>) complex and characterization of a proposed oxodicobalt(<scp>ii</scp>) intermediate

Reduction of CO2 by a masked two-coordinate cobalt(i) complex and characterization of a proposed oxodicobalt(ii) intermediate

Reduction of CO₂ by a masked two-coordinate cobalt(i) complex and characterization of a proposed oxodicobalt(ii) intermediate