Catalytic Production of Isocyanates via Orthogonal Atom and Group Transfers Employing a Shared Formal Group 6 M(II)/M(IV) Redox Cycle

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• 作者：Brendan L. Yonke ; Jonathan P. Reeds ; Philip P. Fontaine ; Peter Y. Zavalij ; Lawrence R. Sita
• 刊名：Organometallics
• 出版年：2014
• 出版时间：July 14, 2014
• 年：2014
• 卷：33
• 期：13
• 页码：3239-3242
• 全文大小：294K
• ISSN：1520-6041

文摘

Under an atmosphere of CO, the Mo(IV) imido complex Cp*Mo[N(ⁱPr)C(Me)N(ⁱPr)](NSiMe₃) (Cp* = 畏⁵-C₅Me₅) (1) serves as a catalyst for production of an isocyanate via metal-mediated nitrene group transfer in benzene solution under mild conditions (55 掳C, 10 psi) according to RN₃ + CO 鈫?N₂ + RNCO. Mechanistic and structural studies support a catalytic cycle for nitrene group transfer involving formal Mo(II) monocarbonyl and Mo(IV) (魏²-C,N)-isocyanate intermediates. These results complement an earlier finding that catalytic production of isocyanates can alternatively proceed through oxygen-atom transfer and an isomeric Mo(IV) (魏²-C,O)-isocyanate according to N₂O + CNR 鈫?N₂ + RNCO.