2003
DOI: 10.1002/hlca.200390112
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Comparing Intrinsic Reactivities of the First‐ and Second‐Generation Ruthenium Metathesis Catalysts in the Gas Phase

Abstract: Dedicated to Professor Jack D. Dunitz on the occasion of his 80th birthday An experimental comparison of the gas-phase reactivity of the 14-electron reactive intermediates produced by phosphine dissociation from the first-and second-generation ruthenium metathesis catalysts, (L)Cl 2 RuCHR (L PCy 3 or NHC), supports Grubbs×s contention that the second-generation catalysts show hundred-fold higher phenomenological activity despite a slower phosphine dissociation because of a much more-favorable partitioning of t… Show more

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Cited by 57 publications
(48 citation statements)
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“…Experiments show that the phosphine dissociation in (PCy 3 ) 2 Cl 2 Ru = CHPh is faster than in (H 2 IMes)(PCy 3 )Cl 2-Ru = CHPh [138,139], where Cy, Ph, and IMes are cyclohexyl, phenyl, and 1,3-dimesitylimidazol-2-ylidine. We have shown [16,140] that the M06 suite of functionals predict the right trend of bond dissociation energies (BDEs) whereas B3LYP and other popular functionals predict the wrong trend for the BDE difference.…”
Section: Organometallic Complexes and Catalysismentioning
confidence: 98%
“…Experiments show that the phosphine dissociation in (PCy 3 ) 2 Cl 2 Ru = CHPh is faster than in (H 2 IMes)(PCy 3 )Cl 2-Ru = CHPh [138,139], where Cy, Ph, and IMes are cyclohexyl, phenyl, and 1,3-dimesitylimidazol-2-ylidine. We have shown [16,140] that the M06 suite of functionals predict the right trend of bond dissociation energies (BDEs) whereas B3LYP and other popular functionals predict the wrong trend for the BDE difference.…”
Section: Organometallic Complexes and Catalysismentioning
confidence: 98%
“…But the mechanistic discussion is still going on. Chen et al conducted electrospray ionization tandem mass spectroscopy investigations [160][161][162][163] and concluded that the metallacyclobutane is a transition state rather than an intermediate, while calculations by Bottoni et al found it to be an intermediate [164]. Additionally several other reaction pathways and intermediates have been proposed [118,[165][166][167][168][169][170], but there is still the need to collect additional data before a definitive answer on the mechanism of olefin metathesis catalysed by Grubbs/Herrmann catalysts can be given.…”
Section: Grubbs/herrmann Metathesis Catalystsmentioning
confidence: 99%
“…Ruthenium-carbene catalysts were studied mechanistically both in solution [14][15][16][17][18] and in the gas phase. [19][20][21][22][23] There is substantial evidence [17][18][19][20][21] that the reaction favors the dissociative pathway, that is, the reactive catalytic species formed from pentacoordinate [(PR 3 [18] Such issues can be examined by means of quantum-chemical calculations. Until recently, theoretical calculations on olefin metathesis remained scarce.…”
Section: Introductionmentioning
confidence: 99%