Determinant Role of Electrogenerated Reactive Nucleophilic Species on Selectivity during Reduction of CO(2) Catalyzed by Metalloporphyrins

[Image: see text] This work provides insights to understand the selectivity during the reduction of CO(2) with metalloporphyrin (MP) catalysts. The attack of a nucleophile on the carbon of the CO(2) appears as an important event that triggers the catalytic reaction, and the nature of this nucleophile determines the selectivity between CO (or further reduced species) and HCOOH/HCOO(–). For MP, the possible electrogenerated nucleophiles are the reduced metal-center and the hydride donor species, metal-hydride and phlorin-hydride ligand. The reduced metal-center activates the CO(2) with the formation of the metal–carbon bond, which then gives rise to the formation of CO. The hydride donor species trigger the CO(2) reduction by the attack of the hydride on the carbon of the CO(2) (formation of a C–H bond), which results in the formation of HCOOH/HCOO(–) (formation of the metal-bonded formate intermediate is not involved). The MP with the metals Ni, Cu, Zn, Pd, Ag, Cd, Ga, In, and Sn are predicted to only form the phlorin-hydride intermediate and are thus suitable to produce HCOOH/HCOO(–). This agrees well with the available experimental results. The MP with the metals Fe, Co, and Rh can form both the reduced-metal center and the hydride donor species (metal-hydride and phlorin-hydride), and thus are able to form both CO and HCOOH/HCOO(–). The production of CO for Fe and Co is indeed observed experimentally, but not for Rh, probably due to the presence of axial ligands that may hinder the formation of the metal-bonded intermediates and thus drive the CO2RR to HCOOH/HCOO(–) via the phlorin intermediate.