Synthesis, Structure, and Solution Behavior of 1-Chloro-2,2-difluorovinyl Titanocene Derivatives: The First X-ray Study of a Titanium Fluorovinyl Compound and Spectroscopic Elucidation of the [Cp

详细信息    查看全文

• 作者：Nicholas A. Barnes ; Alan K. Brisdon ; Ian R. Crossley ; Robin G. Pritchard ; and John E. Warren
• 刊名：Organometallics
• 出版年：2004
• 出版时间：May 24, 2004
• 年：2004
• 卷：23
• 期：11
• 页码：2680 - 2685
• 全文大小：116K
• 年卷期：v.23,no.11(May 24, 2004)
• ISSN：1520-6041

文摘

The first early-transition-metal 1-chloro-2,2-difluorovinyl complexes [Cp₂TiX_n(CCl=CF₂)_2-n](X = Cl, F; n = 0, 1) have been synthesized by the low-temperature reaction of Cp₂TiX₂(X = Cl, F) with (1-chloro-2,2-difluorovinyl)lithum, generated in situ from HCFC-133a (CF₃CH₂Cl) and n-butyllithium. The complexes have been characterized by spectroscopy and, inthe case of [Cp₂TiCl(CCl=CF₂)], by single crystal X-ray diffraction, making this the firststructurally characterized titanium-based fluorovinyl compound. The marked solution-phaseinstability of these materials has been explored in an attempt to identify key characteristicsthat might lead to stabilized systems. To this end, syntheses of the compounds [Cp*₂TiF_n(CF=CF₂)_2-n] (n = 0, 1) and [Cp₂TiMe(CCl=CF₂)] have been reported and their stabilitiesinvestigated further. In the case of [Cp₂TiMe(CCl=CF₂)], this has led to the spectroscopiccharacterization of the mages/gifchars/pi.gif" BORDER=0 >-complex [Cp₂TiMe(mages/gifchars/eta.gif" BORDER=0 >²-CF₂=CClH)] as an intermediate in thesolution-phase decomposition pathway.