Despite renewed interest in carbon dioxide (CO2) reduction chemistry, examples of homogeneous iron catalysts that hydrogenate CO2 are limited compared to their noble-metal counterparts. Knowledge of the thermodynamic properties of iron hydride complexes, including M–H hydricities (ΔGH–), could aid in the development of new iron-based catalysts. Here we present the experimentally determined hydricity of an iron hydride complex: (SiPiPr3)Fe(H2)(H), ΔGH– = 54.3 ± 0.9 kcal/mol [SiPiPr3 = [Si(o-C6H4PiPr2)3]−]. We also explore the CO2 hydrogenation chemistry of a series of triphosphinoiron complexes, each with a distinct apical unit on the ligand chelate (Si–, C–, PhB–, N, B). The silyliron (SiPR3)Fe (R = iPr and Ph) and boratoiron (PhBPiPr3)Fe (PhBPiPr3 = [PhB(CH2PiPr2)3]−) systems, as well as the recently reported (CPiPr3)Fe (CPiPr3 = [C(o-C6H4PiPr2)3]−), are also catalysts for CO2 hydrogenation in methanol and in the presence of triethylamine, generating methylformate and triethylammonium formate at up to 200 TON using (SiPPh3)FeCl as the precatalyst. Under stoichiometric conditions, the iron hydride complexes of this series react with CO2 to give formate complexes. Finally, the proposed mechanism of the (SiPiPr3)-Fe system proceeds through a monohydride intermediate (SiPiPr3)Fe(H2)(H), in contrast to that of the known and highly active tetraphosphinoiron, (tetraphos)Fe (tetraphos = P(o-C6H4PPh2)3), CO2 hydrogenation catalyst.
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