Fe(I)-Mediated Reductive Cleavage and Coupling of CO₂:  An Fe^II(μ-O,μ-CO)Fe^II Core

Abstract

THF solutions of a new iron(I) source, [PhBP CH 2 Cy 3 ]Fe ([PhBP CH 2 Cy 3 ] = [PhBP(CH 2 P(CH 2 Cy) 2 ) 3 ] - ), effect the reductive cleavage of CO 2 via O-atom transfer at ambient temperature. The dominant reaction pathway is bimetallic and leads to the formation of a structurally unprecedented diiron Fe II (μ-O)(μ-CO)Fe II core. X-ray data are also available to suggest that bimetallic reductive CO 2 coupling to generate oxalate occurs as a minor reaction pathway. These initial observations forecast a diverse reaction landscape between CO 2 and iron(I) synthons.