Dirhodium complexes as electrocatalysts for CO2 reduction to HCOOH: role of steric hindrance on selectivity

Abstract

A series of Rh₂(II,II) complexes were shown to electrocatalytically reduce CO₂ to HCOOH. Electrochemical and spectroelectrochemical studies reveal a correlation between catalytic selectivity and efficiency with the steric bulk at the axial sites afforded by the bridging ligands. Mechanistic studies point to the presence of a Rh₂(II,I)–H hydride as a key intermediate in the catalytic cycle.