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17O-labelled tungsten siloxide complexes [WOCl2(OSitBu3)2] (1-Cl) and [WOMe2(OSitBu3)2] (1-Me) were prepared and characterized by 17O MAS NMR, with input from theoretical calculations of NMR parameters. Guidelines linking 17O NMR parameters and the coordination sphere of molecular and silica-grafted tungsten oxo species are proposed. The grafting of 1-Me on SiO2-700 afforded material 2, with surface species [(≡SiO)WOMe2(OSitBu3)] as shown by elemental analysis, IR and 1H and 13C MAS NMR. The DFT calculations of the grafting mechanism are in line with the observed reactivity. They indicate the occurrence of several isomeric species of close energy for the grafted W centers, precluding efficient 17O MAS NMR studies. The lack of catalytic activity in olefin metathesis and ring-opening olefin metathesis polymerization indicates that initiation by α-H elimination is not operative in 2, contrary to related tungsten surface species, which illustrates the crucial influence of the nature of the metal coordination sphere. [ABSTRACT FROM AUTHOR]