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Bulky Aryloxide Ligand Stabilizes a Heterogeneous Metathesis Catalyst
Author(s) -
Conley Matthew P.,
Forrest William P.,
Mougel Victor,
Copéret Christophe,
Schrock Richard R.
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201408880
Subject(s) - metathesis , alkene , metallacycle , catalysis , ligand (biochemistry) , chemistry , ethylene , salt metathesis reaction , polymer chemistry , photochemistry , organic chemistry , polymerization , polymer , x ray crystallography , biochemistry , physics , receptor , diffraction , optics
The reaction of [W(O)(CHCMe 2 Ph)(dAdPO) 2 ], containing bulky 2,6‐diadamantyl aryloxide ligands, with partially dehydroxylated silica selectively yields a well‐defined silica‐supported alkylidene complex, [(SiO)W(O)(CHCMe 2 Ph)(dAdPO)]. This fully characterized material is a very active and stable alkene metathesis catalyst, thus allowing loadings as low as 50 ppm in the metathesis of internal alkenes. [(SiO)W(O)(CHCMe 2 Ph)(dAdPO)] also efficiently catalyzes the homocoupling of terminal alkenes, with turnover numbers exceeding 75 000 when ethylene is constantly removed to avoid the formation of the less reactive square‐based pyramidal metallacycle resting state.