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A Comparison of the Activity of Homogeneous Tungsten and Ruthenium Catalysts for the Metathesis of 1‐Octene
Author(s) -
van Schalkwyk C.,
Vosloo H. C. M.,
du Plessis J. A. K.
Publication year - 2002
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/1615-4169(200208)344:6/7<781::aid-adsc781>3.0.co;2-8
Subject(s) - chemistry , metathesis , catalysis , ruthenium , alkene , selectivity , alkoxide , salt metathesis reaction , tungsten , solvent , ring opening metathesis polymerisation , medicinal chemistry , polymer chemistry , organic chemistry , polymerization , polymer
The W(O‐2,6‐C 6 H 3 X 2 ) 2 Cl 4 /Bu 4 Sn catalytic systems (X=Ph, F, Cl, Br) have a high activity for the metathesis of terminal alkenes and a high selectivity towards primary metathesis products. Tungsten(VI) alkoxide complexes are not nearly as active as the tungsten(VI) aryloxide complexes. Brønsted acids such as HOAc, BuOH and H 2 O deactivate both the W(O‐2,6‐C 6 H 3 X 2 ) 2 Cl 4 /Bu 4 Sn (X=Cl and Ph) catalytic systems. The Lewis base (BuOAc) showed no deactivation of the catalytic systems. The Grubbs catalyst, RuCl 2 (PCy 3 ) 2 (CHPh), is very active for the metathesis of 1‐alkenes, even at an alkene/Ru molar ratio=100,000. Selectivities >93% were generally obtained. The ruthenium catalyst is active at low temperatures (25 °C) and high temperatures (130 °C). It shows a high tolerance towards oxygen‐containing additives. The polarity of the solvent plays a major role in the activity and also the selectivity of especially the W(O‐2,6‐C 6 H 3 X 2 ) 2 Cl 4 /Bu 4 Sn catalytic systems.