Carbon Monoxide-Induced N鈥揘 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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• 作者：Jonathan P. Reeds ; Brendan L. Yonke ; Peter Y. Zavalij ; Lawrence R. Sita
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：November 23, 2011
• 年：2011
• 卷：133
• 期：46
• 页码：18602-18605
• 全文大小：754K
• 年卷期：v.133,no.46(November 23, 2011)
• ISSN：1520-5126

文摘

In the presence of CO, facile N鈥揘 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* = 畏⁵-C₅Me₅) (1) and {Cp*Mo[N(ⁱPr)C(Me)N(ⁱPr)]}₂(渭-畏¹:畏¹-N₂) (9) under photolytic and dark conditions, respectively, to produce the nitrosyl, isocyanate complex Cp*Mo[N(ⁱPr)C(Me)N(ⁱPr)](魏-N-NO)(魏-N-NCO) (7). Competitive N鈥揙 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.