Strongly σ Donating Thiophenoxide in Silica-Supported Tungsten Oxo Catalysts for Improved 1‑Alkene Metathesis Efficiency

Strongly σ Donating Thiophenoxide in Silica-Supported Tungsten Oxo Catalysts for Improved 1‑Alkene Metathesis Efficiency

We report the synthesis of tungsten oxo alkylidene complexes bearing bulky thiophenoxide ligands [W(O)(CHtBu)(SHMT)2(PMe2Ph)] and [W(O)(CHtBu)(SHMT)2] (SHMT = 2,6-dimesitylthiophenoxide) and their grafting on partially dehydroxylated silica, affording the supported complexes [(SiO)W(O)(CHtBu)...

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Bibliographic Details
Published in:Organometallics Vol. 34; no. 3; pp. 551 - 554
Main Authors: Mougel, Victor, Pucino, Margherita, Copéret, Christophe
Format: Journal Article
Language:English
Published: American Chemical Society 09-02-2015
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Summary:We report the synthesis of tungsten oxo alkylidene complexes bearing bulky thiophenoxide ligands [W(O)(CHtBu)(SHMT)2(PMe2Ph)] and [W(O)(CHtBu)(SHMT)2] (SHMT = 2,6-dimesitylthiophenoxide) and their grafting on partially dehydroxylated silica, affording the supported complexes [(SiO)W(O)(CHtBu)(SHMT)(PMe2Ph)] and [(SiO)W(O)(CHtBu)(SHMT)]. While the molecular precursors are not significantly active in the metathesis of alkenes, the grafted analogue without bound phosphine ligands displays activity comparable to that of its aryloxide analogue [(SiO)W(O)(CHtBu)(OHMT)] (OHMT = 2,6-dimesitylphenoxide). It is worth noting that [(SiO)W(O)(CHtBu)(SHMT)] showed unprecedented activity in the metathesis of 1-alkenes, probably because of the lower stability of metallacyclobutane intermediates.
ISSN:0276-7333
1520-6041
DOI:10.1021/om5013105