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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

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journal contribution
posted on 2016-02-22, 13:46 authored by Jonathan P. Reeds, Brendan L. Yonke, Peter Y. Zavalij, Lawrence R. Sita
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-η11-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.