Carbon Monoxide-Induced N–N Bond Cleavage of Nitrous Oxide That Is Competitive with Oxygen Atom Transfer to Carbon Monoxide As Mediated by a Mo(II)/Mo(IV) Catalytic Cycle

In the presence of CO, facile N–N bond cleavage of N₂O occurs at the formal Mo(II) center within coordinatively unsaturated mononuclear species derived from Cp*Mo[N(ⁱPr)C(Me)N(ⁱPr)](CO)₂ (Cp* = η⁵-C₅Me₅) (1) and {Cp*Mo[N(ⁱPr)C(Me)N(ⁱPr)]}₂(μ-η¹:η¹-N₂) (9) under photolytic and dark conditions, respectively, to produce the nitrosyl, isocyanate complex Cp*Mo[N(ⁱPr)C(Me)N(ⁱPr)](κ-N-NO)(κ-N-NCO) (7). Competitive N–O bond cleavage of N₂O proceeds under the same conditions to yield the Mo(IV) terminal metal oxo complex Cp*Mo[N(ⁱPr)C(Me)N(ⁱPr)](O) (3), which can be recycled to produce more 7 through oxygen-atom-transfer oxidation of CO to produce CO₂.