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((i)Prr)C(Me)N(Pr-i)] (CO)(2) (Cp* =eta(5)-C5Me5) (1) and {Cp*Mo[N(Pr-i)C(Me)N(Pr-i)]}(2)(mu-eta(1:)eta(1)-N-2) (9) under photolytic and dark conditions, respectively, to produce the nitrosyl, isocyanate complex Cp*Mo[N(Pr-i)C(Me)N(Pr-i)]-(kappa-N-NCO) (kappa-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(Pr-i)C(Me)-N(Pr-i)] (O) (3), which can be recycled to produce more 7 through oxygen-atom-transfer oxidation of CO to produce CO2.