Mechanism of the Generation of Ketenimine-M(CO)n Complexes (M = Cr, W, Fe) from Fischer Carbenes and Isocyanides

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• 作者：Israel Fern&aacute ; ndez ; Fernando P. Cossí ; o ; Miguel A. Sierra
• 刊名：Organometallics
• 出版年：2007
• 出版时间：June 4, 2007
• 年：2007
• 卷：26
• 期：12
• 页码：3010 - 3017
• 全文大小：471K
• 年卷期：v.26,no.12(June 4, 2007)
• ISSN：1520-6041

文摘

The mechanism of the thermal formation of ketenimine complexes through the reaction of group 6(chromium and tungsten) and 8 (iron) Fischer carbenes and isocyanides has been studied computationallywithin the density functional theory framework. The computational data have been compared to the reportedexperimental results. It is found that the insertion of the Nmages/entities/tbd1.gif">C bond of the isocyanide into the M=Cbond of the Fischer carbene complexes, which leads to N-metalated-ketenimine complexes, occurs viametallacyclopropanimine species, rather than the proposed ylide complexes, followed by isomerizationand 1,2-metallotropic rearrangement. We also studied the 6mages/gifchars/pi.gif" BORDER=0 >-electrocyclization process of dienyl-ketenimine complexes, which leads to o-alkoxy aniline compounds. In terms of the synchronicity, activationenergy, and aromaticity, the effect of the metal in this electrocyclization transformation is almost negligible.