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(ll)/Mo(IV) Catalytic Cycle

摘要

In the presence of CO, facile N-N bond cleavage of N_2O occurs at the formal Mo(Il) center within coordinatively unsaturated mononuclear species derived from Cp*Mo[N(iPr)C(Me)N(iPr)](CO)_2 (Cp* = η ~5-C_5Me_5) (1) and {Cp~*Mo[N(i~Pr)C(Me)N(i~Pr)]}_2(μ-η~1:η~1-N_2) (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 N_2O proceeds under the same conditions to yield the Mo(PvO terminal metal oxo complex Cp~*Mo[N(i~Pr)C(Me)-N(i~Pr)](O) (3), which can be recycled to produce more 7 through oxygen-atom-transfer oxidation of CO to produce CO_2.