The grafting of an oxo chloro trisalkyl tungsten derivative on silica'. dehydroxylated at 700 C was Studied by several techniques that showed reaction via W-Cl cleavage, to afford, a well-defined precatalyst for alkene metathesis. This was further confirmed by DFT calculations on the grafting process. 170 labeling of the oxo moiety of a series of related molecular and supported tungsten oxo derivatives was achieved, and the corresponding 170 MAS NMR spectra were recorded. Combined experimental and theoretical NM R studies yielded information on the local structure of the surface species. Assessment of the 170 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.