Publication type: Article in scientific journal
Type of review: Peer review (publication)
Title: Comparing intrinsic reactivities of the first- and second-generation ruthenium metathesis catalysts in the gas phase
Authors: Adlhart, Christian
Chen, Peter
DOI: 10.1002/hlca.200390112
Published in: Helvetica Chimica Acta
Volume(Issue): 86
Issue: 4
Pages: 941
Pages to: 949
Issue Date: 29-Apr-2003
Publisher / Ed. Institution: Wiley
Publisher / Ed. Institution: Weinheim
ISSN: 0018-019X
Language: English
Subjects: Metathesis catalysts; Reactivity; Transition state structure; Exothermic reaction
Subject (DDC): 540: Chemistry
660: Chemical engineering
Abstract: An exptl. comparison of the gas-phase reactivity of the 14-electron reactive intermediates produced by phosphine dissocn. from the first- and second-generation ruthenium metathesis catalysts, (L)Cl2Ru=CHR (L = PCy3 or NHC), supports Grubbs's contention that the second-generation catalysts show hundred-fold higher phenomenol. activity despite a slower phosphine dissocn. because of a much more favorable partitioning of the 14-electron active species towards product-forming steps. The gas-phase study finds, in ring-opening metathesis of norbornene as well as acyclic metathesis of Et vinyl ether, that the first-generation systems display evidence for a higher barrier above that for phosphine dissocn.; the second-generation systems, on the other hand, behave as if there is no significantly higher barrier.
Fulltext version: Published version
License (according to publishing contract): Licence according to publishing contract
Departement: Life Sciences and Facility Management
Organisational Unit: Institute of Chemistry and Biotechnology (ICBT)
Appears in Collections:Publikationen Life Sciences und Facility Management

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