Considering a Possible Role for [H-Fe₄N(CO)₁₂]^2– in Selective Electrocatalytic CO₂ Reduction to Formate by [Fe₄N(CO)₁₂]⁻

[Fe₄N­(CO)₁₂]⁻ is a first-row transition element electrocatalyst that selectively produces C–H bonds to give formate from CO₂ in water at −1.2 V vs SCE. We present a thermochemical analysis which probes the possibility that [H-Fe₄N­(CO)₁₂]^2– ((H-1)^2–) is an intermediate in this process: we show that (H-1)^2– is accessible at −1.2 V vs SCE, but if it were formed, we predict that it would generate H₂. [Fe₄N­(CO)₁₂]^3– and (H-1)^2– were interrogated spectroscopically, and the product of CO loss, [Fe₄N­(CO)₉(μ-CO)₂]^3–, was synthesized and characterized. Ultimately, we demonstrate that (H-1)^2– is an unlikely participant in the catalytic transformation of CO₂ to formate.