Title: Comparing intrinsic reactivities of the first- and second-generation ruthenium metathesis catalysts in the gas phase
Authors : Adlhart, Christian
Chen, Peter
Published in : Helvetica Chimica Acta
Volume(Issue) : 86
Issue : 4
Pages : 941
Pages to: 949
Publisher / Ed. Institution : Wiley VCH
Publisher / Ed. Institution: Weinheim
Issue Date: 29-Apr-2003
License (according to publishing contract) : Licence according to publishing contract
Type of review: Peer review (Publication)
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.
Departement: Life Sciences und Facility Management
Organisational Unit: Institute of Chemistry and Biotechnology (ICBT)
Publication type: Article in scientific Journal
DOI : 10.1002/hlca.200390112
ISSN: 0018-019X
URI: https://digitalcollection.zhaw.ch/handle/11475/2097
Appears in Collections:Publikationen Life Sciences und Facility Management

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