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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 2 RR and CO 2 RR, respectively) using H + /e - currency. Here we explore, via DFT calculations, three iron model systems, P 3  E Fe (E = B, Si, C), known to mediate both N 2 RR 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 2 RR trend with the predicted N-H bonds strengths of two putative hydrazido intermediates of the proposed catalytic cycle, P 3  E Fe(NNH 2 ) + and P 3  E Fe(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  E Fe(NNH 2 ) species, factors that trend with overall product selectivity.

acs catalysis

Fe-Mediated HER vs N2RR: Exploring Factors That Contribute to Selectivity in P3EFe(N2) (E = B, Si, C) Catalyst Model Systems