Selective Oxidation of H₂ and CO by NiIr Catalyst in Aqueous Solution: A DFT Mechanistic Study

One of the challenges in utilizing hydrogen gas (H₂) as a sustainable fossil fuel alternative is the inhibition of H₂ oxidation by carbon monoxide (CO), which is involved in the industrial production of H₂ sources. To solve this problem, a catalyst that selectively oxidizes either CO or H₂ or one that co-oxidizes H₂ and CO is needed. Recently, a NiIr catalyst [Ni^IICl(X)Ir^IIICl(η⁵-C₅Me₅)], (X = N,N'-dimethyl-3,7-diazanonane-1,9-dithiolate), which efficiently and selectively oxidizes either H₂ or CO depending on the pH, has been developed (Angew. Chem. Int. Ed. 2017, 56, 9723-9726). In the present work, density functional theory (DFT) calculations are employed to elucidate the pH-dependent reaction mechanisms of H₂ and CO oxidation catalyzed by this NiIr catalyst. During H₂ oxidation, our calculations suggest that dihydrogen binds to the Ir center and generates an Ir(III)-dihydrogen complex, followed by subsequent isomerization to an Ir(V)-dihydride species. Then, a proton is abstracted by a buffer base, CH₃COO^-, resulting in the formation of a hydride complex. The catalytic cycle completes with electron transfer from the hydride complex to a protonated 2,6-dichlorobenzeneindophenol (DCIP) and a proton transfer from the oxidized hydride complex to a buffer base. The CO oxidation mechanism involves three distinct steps, i.e., (1) formation of a metal carbonyl complex, (2) formation of a metallocarboxylic acid, and (3) conversion of the metallocarboxylic acid to a hydride complex. The formation of the metallocarboxylic acid involves nucleophilic attack of OH^- to the carbonyl-C followed by a large structural change with concomitant cleavage of the Ir-S bond and rotation of the COOH group along the NiIr axis. During the conversion of the metallocarboxylic acid to the hydride complex, intramolecular proton transfer followed by removal of CO₂ leads to the formation of the hydride complexes. In addition, the barrier heights for the binding of small molecules (H₂, OH^-, H₂O, and CO) to Ir were calculated, and the results indicated that dissociation from Ir is a faster process than the binding of H₂O and H₂. These calculations indicate that H₂ oxidation is inhibited by CO and OH^- and thus prefers acidic conditions. In contrast, the CO oxidation reactions occur more favorably under basic conditions, as the formation of the metallocarboxylic acid involves OH^- attack to a carbonyl-C and the binding of OH^- to Ni largely stabilizes the triplet spin state of the complex. Taken together, these calculations provide a rationale for the experimentally observed pH-dependent, selective oxidations of H₂ and CO.