d10 Nickel Difluorocarbenes and Their Cycloaddition Reactions with Tetrafluoroethylene

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• 作者：Daniel J. Harrison ; Alex L. Daniels ; Ilia Korobkov ; R. Tom Baker
• 刊名：Organometallics
• 出版年：2015
• 出版时间：December 28, 2015
• 年：2015
• 卷：34
• 期：24
• 页码：5683-5686
• 全文大小：298K
• ISSN：1520-6041

文摘

We report the first isolable nickel difluorocarbene complexes (NiP₂[P(OMe)₃](═CF₂); P₂ = Ph₂P(CH₂)₂PPh₂, 2 P(OMe)₃), which are also the only examples of formally d¹⁰ metal fluorocarbenes. These [Ni⁰]═CF₂ complexes react with tetrafluoroethylene (TFE) to yield the rare perfluorometallacyclobutanes [NiP₂(κ²-CF₂CF₂CF₂?)], with potential relevance to fluoroalkene metathesis and polymerization. Preliminary kinetic experiments establish that the reactions of the new [Ni]═CF₂ compounds with TFE are considerably faster than the analogous reactions of their previously reported [Co]═CF₂ counterparts. Further, we show that TFE addition to 2 is a dissociative process, in contrast to [Co]═CF₂, which reacts with TFE in an associative fashion. Finally, the preliminary reactivity of NiP₂(κ²-CF₂CF₂CF₂?) (P₂ = Ph₂P(CH₂)₂PPh₂) is described.