Computational Evaluation of Potential Molecular Catalysts for Nitrous Oxide Decomposition

Nitrous oxide (N₂O) is a potent greenhouse gas (GHG) with limited use as a mild anesthetic and underdeveloped reactivity. Nitrous oxide splitting (decomposition) is critical to its mitigation as a GHG. Although heterogeneous catalysts for N₂O decomposition have been developed, highly efficient, long-lived solid catalysts are still needed, and the details of the catalytic pathways are not well understood. Reported herein is a computational evaluation of three potential molecular (homogeneous) catalysts for N₂O splitting, which could aid in the development of more active and robust catalysts and provide deeper mechanistic insights: one Cu(I)-based, [(CF₃O)₄Al]Cu (A-1), and two Ru(III)-based, Cl(POR)Ru (B-1) and (NTA)Ru (C-1) (POR = porphyrin, NTA = nitrilotriacetate). The structures and energetic viability of potential intermediates and key transition states are evaluated according to a two-stage reaction pathway: (A) deoxygenation (DO), during which a metal-N₂O complex undergoes N-O bond cleavage to produce N₂ and a metal-oxo species and (B) (di)oxygen evolution (OER), in which the metal-oxo species dimerizes to a dimetal-peroxo complex, followed by conversion to a metal-dioxygen species from which dioxygen dissociates. For the (F-L)Cu(I) activator (A-1), deoxygenation of N₂O is facilitated by an O-bound (F-L)Cu-O-N₂ or better by a bimetallic N,O-bonded, (F-L)Cu-NNO-Cu(F-L) complex; the resulting copper-oxyl (F-L)Cu-O is converted exergonically to (F-L)Cu-(η²,η²-O₂)-Cu(F-L), which leads to dioxygen species (F-L)Cu(η²-O₂), that favorably dissociates O₂. Key features of the DO/OER process for (POR)ClRu (B-1) include endergonic N₂O coordination, facile N₂ evolution from LR'u-N₂O-RuL to Cl(POR)RuO, moderate barrier coupling of Cl(POR)RuO to peroxo Cl(POR)Ru(O₂)Ru(POR)Cl, and eventual O₂ dissociation from Cl(POR)Ru(η¹-O₂), which is nearly thermoneutral. N₂O decomposition promoted by (NTA)Ru(III) (C-1) can proceed with exergonic N₂O coordination, facile N₂ dissociation from (NTA)Ru-ON₂ or (NTA)Ru-N₂O-Ru(NTA) to form (NTA)Ru-O; dimerization of the (NTA)Ru-oxo species is facile to produce (NTA)Ru-O-O-Ru(NTA), and subsequent OE from the peroxo species is moderately endergonic. Considering the overall energetics, (F-L)Cu and Cl(POR)Ru derivatives are deemed the best candidates for promoting facile N₂O decomposition.