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