On the Track to Silica-Supported Tungsten Oxo Metathesis Catalysts: Input from 17O Solid-State NMR

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• 作者：Nicolas Merle ; Guillaume Girard ; Nicolas Popoff ; Aimery De Mallmann ; Yassine Bouhoute ; Julien Tr茅bosc ; Elise Berrier ; Jean-Fran莽ois Paul ; Christopher P. Nicholas ; Iker Del Rosal ; Laurent Maron ; R茅gis M. Gauvin ; Laurent Delevoye ; Mostafa Taoufik
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：September 3, 2013
• 年：2013
• 卷：52
• 期：17
• 页码：10119-10130
• 全文大小：565K
• 年卷期：v.52,no.17(September 3, 2013)
• ISSN：1520-510X

文摘

The grafting of an oxo chloro trisalkyl tungsten derivative on silica dehydroxylated at 700 掳C was studied by several techniques that showed reaction via W鈥揅l cleavage, to afford a well-defined precatalyst for alkene metathesis. This was further confirmed by DFT calculations on the grafting process. ¹⁷O labeling of the oxo moiety of a series of related molecular and supported tungsten oxo derivatives was achieved, and the corresponding ¹⁷O MAS NMR spectra were recorded. Combined experimental and theoretical NMR studies yielded information on the local structure of the surface species. Assessment of the ¹⁷O NMR parameters also confirmed the nature of the grafting pathway by ruling out other possible grafting schemes, thanks to highly characteristic anisotropic features arising from the quadrupolar and chemical shift interactions.