On the use of 17 O NMR for understanding molecular and silica-grafted tungsten oxo siloxide complexes

O-labelled tungsten siloxide complexes [WOCl (OSi Bu ) ] (1-Cl) and [WOMe (OSi Bu ) ] (1-Me) were prepared and characterized by O MAS NMR, with input from theoretical calculations of NMR parameters. Guidelines linking O NMR parameters and the coordination sphere of molecular and silica-grafted tungs...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2023-07, Vol.52 (28), p.9573-9581
Main Authors: Bouhoute, Y, Grekov, D, Merle, N, Szeto, K C, Larabi, C, Del Rosal, I, Maron, L, Delevoye, L, Gauvin, R M, Taoufik, M
Format: Article
Language:English
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Chemical Sciences
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Summary:O-labelled tungsten siloxide complexes [WOCl (OSi Bu ) ] (1-Cl) and [WOMe (OSi Bu ) ] (1-Me) were prepared and characterized by O MAS NMR, with input from theoretical calculations of NMR parameters. Guidelines linking O NMR parameters and the coordination sphere of molecular and silica-grafted tungsten oxo species are proposed. The grafting of 1-Me on SiO afforded material 2, with surface species [(SiO)WOMe (OSi Bu )] as shown by elemental analysis, IR and H and C 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 O 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.
ISSN:1477-9226
1477-9234
DOI:10.1039/D3DT01593A