50490-58-9Relevant academic research and scientific papers
A new synthesis of triarylsilylium ions and their application in dihydrogen activation
Schaefer, Andre,Reissmann, Matti,Schaefer, Annemarie,Saak, Wolfgang,Haase, Detlev,Mueller, Thomas
supporting information; experimental part, p. 12636 - 12638 (2012/02/15)
Well-shuffled: An unexpected substituent distribution reaction via alkyldiarylsilylium ions leads to a distribution of substituents. Starting from alkyldiaryl silanes, this reaction provides a facile synthetic approach to sterically highly hindered triarylsilylium ions. These silylium ions can be applied in dihydrogen activation reactions. Copyright
Dimesitylsilyl derivatives of zirconium
Roddick, Dean M.,Heyn, Richard H.,Tilley, T. Don
, p. 324 - 330 (2008/10/08)
The preparation and characterization of (THF)2LiSiHMes2 (1, Mes = mesitvl) are reported. Compound 1 reacts with Cp2Zr(Me)Cl (Cp = η5-C5H5) to afford thermally unstable Cp2Zr(SiHMes2)Me (2), characterized by NMR spectroscopy. Similarly, the reaction of 1 with Cp*2Zr(Me)Br (Cp* = η5-C5Me5) provides the mixed alkyl silyl Cp*2Zr(SiHMes2)Me (3), which is stable for prolonged periods at room temperature. Compound 3 reacts cleanly with 1 equiv of HCl to give the chloro derivative Cp*2Zr(SiHMes2)Cl (4) and methane. Whereas carbon monoxide inserts cleanly into the Zr-C bond of 2, preferential CO insertion into the Zr-Si bond of 3 is observed. These reactions give Cp2Zr(η2-COMe)SiHMes2 (5) and Cp*2Zr-(η2-COSiHMes2)Me (6), respectively. Compound 6 is not stable in solution and slowly isomerizes to the enolate hydride Cp*2Zr[OC(=CH2)SiHMes2]H (7). The mechanism of the latter conversion is discussed. Hydrogen is shown to cleave the Zr-Si bond of 3 faster than the Zr-C bond. Reaction of 3 with AgOSO2CF3 results in oxidative cleavage of the Zr-Si bond giving MeS2HSiSiHMes2, Mes2SiH(OSO2CF3), MeS2SiH(Me), and Cp*2Zr(Me)OSO2CF3 (9), which was independently prepared from Cp*2ZrMe2 and AgOSO2CF3. Reaction of Cp*2ZrCl2 with 2 equiv of 1 does not give a bis(silyl) complex but instead results in dehydrohalogenation to MeS2SiH2 and the metallacycle Cp*2ZrCH2CCHCMeCHCMeCSiHMes (10).
