Reactions of Isocyanides with Metal Carbyne Complexes: Isolation and Characterization of Metallacyclopropenimine Intermediates

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• 作者：Ming Luo ; Lipeng Long ; Hong ZhangYuhui Yang ; Yuhui Hua ; Gang Liu ; Zhenyang LinHaiping Xia
• 刊名：Journal of the American Chemical Society
• 出版年：2017
• 出版时间：February 8, 2017
• 年：2017
• 卷：139
• 期：5
• 页码：1822-1825
• 全文大小：363K
• ISSN：1520-5126

文摘

η²-Iminoketenyl species have often been postulated as the intermediates in nucleophile-induced carbyne–isocyanide C–C coupling processes. However, such species are elusive. Here we report direct formation of η²-iminoketenyl complexes from reactions of metallapentalyne with isocyanides. Our studies show that steric effects of N-substituents of the isocyanides play an important role in the stability of the three-membered metallacycles of the η²-iminoketenyl complexes. Sterically bulky isocyanides, such as tert-butyl or 1-adamantyl isocyanides, inhibit bending at the isocyanide nitrogen atoms, a requirement for formation of η²-iminoketenyl structures. Reactions of metallapentalyne with excess isocyanide allow the metal-bridged metallaindene derivativesto be isolated as a result of the isocyanide insertion into the M–C_α σ bond of metallapentalyne.