Synthesis and Reactions of Ditantalum—Allyl Complexes Derived from Intramolecular C–H Bond Activation of the Methylene of the Ethyl Group Bound to Ditantallacyclopentadiene

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• 作者：Keishi Yamamoto ; Haruki Nagae ; Hayato Tsurugi ; Kazushi Mashima
• 刊名：Organometallics
• 出版年：2016
• 出版时间：July 25, 2016
• 年：2016
• 卷：35
• 期：14
• 页码：2384-2390
• 全文大小：386K
• 年卷期：0
• ISSN：1520-6041

文摘

Reaction of a dinuclear tantallacyclopentadiene complex, Ta₂Cl₆(μ-C₄Et₄) (1), with PhSiH₃ quantitatively afforded a polymeric dinuclear tantalum η³-allyl complex, {Ta₂Cl₅[μ-C₄Et₃(CHMe)]}_n (2), whose η³-allyl moiety was derived from selective C–H bond activation of the methylene moiety of the ethyl group bound to the tantallacyclopentadiene fragment. Lewis bases, such as THF and PMe₂Ph, coordinated to 2 to give Ta₂Cl₅(L)₂[μ-C₄Et₃(CHMe)] (3: L = thf; 4: L = PMe₂Ph). An insertion reaction of diphenylacetylene into the η³-allyl moiety of 3 afforded the diphenylacetylene-incorporated complex 5. Similarly, unsaturated organic substrates, such as trimethylsilylacetylene, 2-vinylpyridine, and benzaldehyde, inserted into the η³-allyl moiety of 3 to afford the corresponding complexes 6–8.