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

THF solutions of a new iron(I) source, [PhBP^CH₂Cy₃]Fe ([PhBP^CH₂Cy₃] = [PhBP(CH₂P(CH₂Cy)₂)₃]^-), effect the reductive cleavage of CO₂ 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 CO₂ coupling to generate oxalate occurs as a minor reaction pathway. These initial observations forecast a diverse reaction landscape between CO₂ and iron(I) synthons.