Isolation and Characterization of a Tetramethyliron(III) Ferrate: An Intermediate in the Reduction Pathway of Ferric Salts with MeMgBr

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• 作者：Malik H. Al-Afyouni ; Kathlyn L. Fillman ; William W. Brennessel ; Michael L. Neidig
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：November 5, 2014
• 年：2014
• 卷：136
• 期：44
• 页码：15457-15460
• 全文大小：286K
• ISSN：1520-5126

文摘

While iron-catalyzed Kumada cross-coupling reactions with simple iron salts have been known since the early 1970s, the nature of the in situ-formed iron species remains elusive. Herein, we report the synthesis of the homoleptic tetralkyliron(III) ferrate complex [MgCl(THF)₅][FeMe₄] from the reaction of FeCl₃ with MeMgBr in THF. Upon warming, this distorted square-planar S = ³/₂ species converts to the S = ¹/₂ species originally observed by Kochi and co-workers with concomitant formation of ethane, consistent with its intermediacy in the reduction pathway of FeCl₃ to generate the reduced iron species involved in catalysis.