Steric and Lewis Basicity Influence of the Second Coordination Sphere on Electrocatalytic CO₂ Reduction by Manganese...

This study aims to provide a greater insight into the balance between steric (bpy vs (Ph)₂bpy vs mes₂bpy ligands) and Lewis basic ((Ph)₂bpy vs (MeOPh)₂bpy vs (MeSPh)₂bpy ligands) influence on the efficiencies of the protonation-first vs reduction-first CO₂ reduction mechanisms with [Mn^I(R₂bpy)(CO)₃(CH₃CN)]⁺ precatalysts, and on their respective transition-state geometries/energies for rate-determining C-OH bond cleavage toward CO evolution. The presence of only modest steric bulk at the 6,6'-diphenyl-2,2'-bipyridyl ((Ph)₂bpy) ligand has here allowed unique insight into the mechanism of catalyst activation and CO₂ binding by navigating a perfect medium between the nonsterically encumbered bpy-based and the highly sterically encumbered mes₂bpy-based precatalysts. Cyclic voltammetry conducted in CO₂-saturated electrolyte for the (Ph)₂bpy-based precatalyst [2-CHCN] confirms that CO₂ binding occurs at the two-electron-reduced activated catalyst [2] in the absence of an excess proton source, in contrast to prior assumptions that all manganese catalysts require a strong acid for CO₂ binding. This observation is supported by computed free energies of the parent-child reaction for [Mn-Mn] dimer formation, where increased steric hindrance relative to the bpy-based precatalyst correlates with favorable CO₂ binding. A critical balance must be adhered to, however, as the absence of steric bulk in the bpy-based precatalyst [1-CHCN] maintains a lower overpotential than [2-CHCN] at the protonation-first pathway with comparable kinetic performance, whereas an ∼2-fold greater TOF_max is observed at its reduction-first pathway with an almost identical overpotential as [2-CHCN]. Notably, excessive steric bulk in the mes₂bpy-based precatalyst [3-CHCN] results in increased activation free energies of the C-OH bond cleavage transition states for both the protonation-first and the reduction-first pathways relative to both [1-CHCN] and [2-CHCN]. In fact, [3-CHCN] requires a 1 V window beyond its onset potential to reach its peak catalytic current, which is in contrast to the narrower (<0.30 V) potential response window of the remaining catalysts here studied. Voltammetry recorded under 1 atm of CO₂ with 2.8 M (5%) H₂O establishes [2-CHCN]⁺ to have the lowest overpotential (η = 0.75 V) in the series here studied, attributed to its ability to lie "on the fence" when providing sufficient steric bulk to hinder (but not prevent) [Mn-Mn] dimerization, while simultaneously having a limited steric impact on the free energy of activation for the rate-determining C-OH bond cleavage transition state. While the methoxyphenyl bpy-based precatalyst [4-CHCN]⁺ possesses an increased steric presence relative to [2-CHCN]⁺, this is offset by its capacity to stabilize the C-OH bond cleavage transition states of both the protonation-first and the reduction-first pathways by facilitating second coordination sphere H-bonding stabilization.