Synthesis, Structure, and Activity of Enhanced Initiators for Olefin Metathesis
Top Cited Papers
- 23 July 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 125 (33) , 10103-10109
- https://doi.org/10.1021/ja027472t
Abstract
A series of ruthenium olefin metathesis catalysts of the general structure (H2IMes)(PR3)(Cl)2RuCHPh (H2IMes = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) have been prepared; these complexes are readily accessible in two steps from commercially available (H2IMes)(PCy3)(Cl)2RuCHPh. Their phosphine dissociation rate constants (k1), relative rates of phosphine reassociation, and relative reaction rates in ring-opening metathesis polymerization (ROMP) and ring-closing metathesis (RCM) have been investigated. The rates of phosphine dissociation (initiation) from these complexes increase with decreasing phosphine donor strength. Complexes containing a triarylphosphine exhibit dramatically improved initiation relative to (H2IMes)(PCy3)(Cl)2RuCHPh. Conversely, phosphine reassociation shows no direct correlation with phosphine electronics. In general, increased phosphine dissociation leads to faster olefin metathesis reaction rates, which is of direct significance to both organic and polymer metathesis processes.Keywords
This publication has 43 references indexed in Scilit:
- A Highly Active and Air-Stable Ruthenium Complex for Olefin Metathesis This work was supported by the Fonds der Chemischen Industrie.Angewandte Chemie International Edition in English, 2002
- Increasing the Initiation Efficiency of Ruthenium-Based Ring-Opening Metathesis Initiators: Effect of Excess PhosphineMacromolecules, 2001
- A Versatile Precursor for the Synthesis of New Ruthenium Olefin Metathesis CatalystsOrganometallics, 2001
- Highly Efficient Ring-Opening Metathesis Polymerization (ROMP) Using New Ruthenium Catalysts Containing N-Heterocyclic Carbene LigandsPublished by Wiley ,2000
- A New and Highly Efficient Grubbs Initiator for Ring-Opening Metathesis PolymerizationMacromolecules, 1999
- A Novel Class of Ruthenium Catalysts for Olefin MetathesisAngewandte Chemie International Edition in English, 1998
- Relative Reaction Rates of Olefin Substrates with Ruthenium(II) Carbene Metathesis Initiators1Organometallics, 1998
- Re-examination of the Metal Carbonyl Complex Infrared Parameter, vco, and Phosphorus Ligand Parameters, pKa, Σχiand Σσph, in Relation to an Evaluation of σ and Ω Components of M-P BondsComments on Inorganic Chemistry, 1996
- Safe and Convenient Procedure for Solvent PurificationOrganometallics, 1996
- Expedient assembly of carbocyclic, heterocyclic, and polycyclic compounds by trimethylstannyl radical mediated carbocyclizations of dienes and trienes: a novel oxidative cleavage of the carbon-tin bondJournal of the American Chemical Society, 1992