Vinylidene Compounds from the Reactions of Me3SiCCSiMe3 with TpMe2Ir Precursors. Protonation to Alky
详细信息 查看全文
- 作者：Kerstin Ilg ; Margarita Paneque ; Manuel L. Poveda ; Nuria Rendó ; n ; Laura L. Santos ; Ernesto Carmona ; and Kurt Mereiter
- 刊名：Organometallics
- 出版年：2006
- 出版时间：April 24, 2006
- 年：2006
- 卷：25
- 期：9
- 页码：2230 - 2236
- 全文大小：137K
- 年卷期：v.25,no.9(April 24, 2006)
- ISSN：1520-6041
文摘
Reaction of the Ir(I) butadiene compound TpMe2Ir(
4-CH2=C(Me)C(Me)=CH2) with the alkyneMe3SiC
CSiMe3 gives the vinylidene TpMe2Ir(CH2C(Me)=C(Me) CH2)(=C=C(SiMe3)2) (1). A relatedvinylidene 2 forms when TpMe2Ir(Ph)2(N2) is reacted with Me3SiCCSiMe3. Compounds 1 and 2 havebeen characterized by microanalysis and spectroscopy (IR, 1H and 13C{1H} NMR data), and in additionthe molecular structure of 1 has been determined by X-ray diffraction. The reactions of these compoundswith different protic acids have been investigated. Thus, the vinylidene 2 gives rise to the cationic alkylidene[TpMe2Ir(Ph)(Et2O)(=C(Me)Ph)]BF4 (3) when treated with HBF4, to the neutral chlorocarbene TpMe2Ir(Ph)(Cl)(=C(Me)Ph) (4) upon reaction with HCl, and to the neutral alkylidene TpMe2Ir(Ph)(
1-O2CCF3)(=C(Me)Ph) (5) by action of CF3COOH. In turn the vinylidene species 1 and CF3COOH give rise to theiridabenzene compound TpMe2Ir(H)(CHC(Me)C(Me)CH C(Me)) (6), characterized in the solid state byX-ray crystallography.
4-CH2=C(Me)C(Me)=CH2) with the alkyneMe3SiCCSiMe3 gives the vinylidene CSiMe3. Compounds 1 and 2 havebeen characterized by microanalysis and spectroscopy (IR, 1H and 13C{1H} NMR data), and in additionthe molecular structure of 1 has been determined by X-ray diffraction. The reactions of these compoundswith different protic acids have been investigated. Thus, the vinylidene 2 gives rise to the cationic alkylidene[TpMe2Ir(Ph)(Et2O)(=C(Me)Ph)]BF4 (3) when treated with HBF4, to the neutral chlorocarbene TpMe2Ir(Ph)(Cl)(=C(Me)Ph) (4) upon reaction with HCl, and to the neutral alkylidene TpMe2Ir(Ph)(1-O2CCF3)(=C(Me)Ph) (5) by action of CF3COOH. In turn the vinylidene species 1 and CF3COOH give rise to theiridabenzene compound