Nitrosoarene-Cu(I) Complexes Are Intermediates in Copper-Catalyzed Allylic Amination

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• 作者：Radhey S. Srivastava ; Masood A. Khan ; and Kenneth M. Nicholas
• 刊名：Journal of the American Chemical Society
• 出版年：2005
• 出版时间：May 25, 2005
• 年：2005
• 卷：127
• 期：20
• 页码：7278 - 7279
• 全文大小：49K
• 年卷期：v.127,no.20(May 25, 2005)
• ISSN：1520-5126

文摘

Reactions of nitrosobenzene and N,N'-diethyl-4-nitrosoaniline with [Cu(CH₃CN)₄]PF₆ produce novel homoleptic Cu(I)-nitrosoarene complexes, [Cu(ArNO)₃]PF₆, 1 (Ar = Ph) and 2 (Ar = 4-Et₂NC₆H₄NO). The X-ray structure of 2 reveals that the copper is coordinated in a severely distorted trigonal planar geometry to the N-atom of the nitrosoarene ligand. Reactions of the PhNO complex 1 with olefins and an olefin/diene mixture provide evidence for its role as an intermediate and possibly the active nitrogen transfer agent in the Cu-catalyzed allylic amination of olefins by aryl hydroxylamines.