Lewis Acid Chemistry of a Cationic [CCH] Subunit in a Bisdisphenoidal Eight-Atom Tetrairon鈥揟etracarbon Cluster

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• 作者：Masaaki Okazaki ; Wataru Taniwaki ; Kazuki Miyagi ; Masato Takano ; Satoshi Kaneko ; Fumiyuki Ozawa
• 刊名：Organometallics
• 出版年：2013
• 出版时间：March 25, 2013
• 年：2013
• 卷：32
• 期：6
• 页码：1951-1957
• 全文大小：435K
• 年卷期：v.32,no.6(March 25, 2013)
• ISSN：1520-6041

文摘

Reaction of [(畏⁵-C₅H₄Me)₄Fe₄(HCCH)(HCCBr)](PF₆) ([2](PF₆)) with AgPF₆ in acetonitrile gave [(畏⁵-C₅H₄Me)₄Fe₄(HCCH)(HCCNCMe)](PF₆)₂ ([3](PF₆)₂). The X-ray diffraction study revealed that the cationic [CCH] subunit is stabilized through coordination of the acetonitrile molecule to the cationic carbon atom. As a synthon for a donor-free [(畏⁵-C₅H₄Me)₄Fe₄(HCCH)(HCC)]²⁺, [(畏⁵-C₅H₄Me)₄Fe₄(HCCH)(HCCL)](PF₆)₂ ([6](PF₆)₂, L = pyrazine) was synthesized by the reaction of [2](PF₆) with AgPF₆ in the presence of pyrazine. Treatment of [6](PF₆)₂ with tertiary amines in acetonitrile led to deprotonation of acetonitrile to form [(畏⁵-C₅H₄Me)₄Fe₄(HCCH)(HCCCH₂CN)](PF₆) ([11](PF₆)). Treatment of [6](PF₆)₂ with maleimide in the presence of tertiary amine in acetonitrile allowed the functionalization of the coordinated acetonitrile through the nucleophilic attack of maleimide at the nitrile carbon atom.