Modification of silica-supported tungsten neosilyl oxo precatalysts: impact of substituted phenol on activity and stability in olefin metathesis

A novel strategy to access a large variety of tungsten oxo pre-catalysts for olefin metathesis involving post-treatment of [(SiO)W(O)(CH 2 SiMe 3 ) 3 ], 1b , with the desired spectator ligands is presented. This method allowed establishing structure–reactivity relationships in propylene metathesis...

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Bibliographic Details
Published in:	Catalysis science & technology 2016-01, Vol.6 (24), p.8532-8539
Main Authors:	Bouhoute, Y., Del Rosal, I., Szeto, K. C., Merle, N., Grekov, D., De Mallmann, A., Le Roux, E., Delevoye, L., Gauvin, R. M., Maron, L., Taoufik, M.
Format:	Article
Language:	eng
Subjects:	Catalysis Chemical Sciences Decomposition reactions Ligands Metathesis Olefins Phenol Spectators Tungsten
Online Access:	Get full text
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Summary:	A novel strategy to access a large variety of tungsten oxo pre-catalysts for olefin metathesis involving post-treatment of [(SiO)W(O)(CH 2 SiMe 3 ) 3 ], 1b , with the desired spectator ligands is presented. This method allowed establishing structure–reactivity relationships in propylene metathesis as a function of the spectator ligands of tungsten oxo species. Thus, the novel pre-catalysts [(SiO)W(O)R 2 X], 2a–c (X = 2,6-dimethylphenoxide, 2-trifluoromethylphenoxide, pentafluorophenoxide), are obtained by modification of well-defined monopodal species 1b by substituted phenols along with TMS release. These were demonstrated by mass balance analysis, elemental analysis, IR, advanced solid-state NMR (1D and 2D 1 H, 13 C and 19 F) and EXAFS. The modified materials were proved to lead to stable and efficient supported tungsten oxo catalysts for propene metathesis under dynamic conditions at 80 °C.
ISSN:	2044-4753 2044-4761