Fe-mediated HER vs N_2RR: Exploring Factors that Contribute to Selectivity in P_3^EFe(N_2) (E = B, Si, C) Catalyst Model Systems

Abstract

Mitigation of the hydrogen evolution reaction (HER) is a key challenge in selective small molecule reduction catalysis. This is especially true of catalytic nitrogen (N_2) and carbon dioxide (CO_2) reduction reactions (N_2RR and CO_2RR, respectively) using H^+/e• currency. Here we explore, via DFT calculations, three iron model systems, P_3^EFe (E = B, Si, C), known to mediate both N_2RR and HER, but with different selectivity depending on the identity of the auxiliary ligand. It is suggested that the respective efficiencies of these systems for N_2RR trend with the predicted N–H bonds strengths of two putative hydrazido intermediates of the proposed catalytic cycle, P_3^EFe(NNH_2)^+ and P_3^EFe(NNH_2). Further, a mechanism is presented for undesired HER consistent with DFT studies, and previously reported experimental data, for these systems; bimolecular proton-coupled-electron-transfer (PCET) from intermediates with weak N–H bonds is posited as an important source of H_2, instead of more traditional scenarios that proceed via metal hydride intermediates and proton transfer/electron transfer (PT/ET) pathways. Wiberg bond indices provide additional insight into key factors related to the degree of stabilization of P_3^EFe(NNH_2) species, factors that trend with overall product selectivity.