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dc.contributor.authorJordaan, M.
dc.contributor.authorVosloo, H.C.M.
dc.date.accessioned2010-05-12T10:30:53Z
dc.date.available2010-05-12T10:30:53Z
dc.date.issued2008
dc.identifier.citationJordaan, M. & Vosloo, H.C.M. 2008. A DFT computational study of phosphine ligand dissociation versus hemilability in a Grubbs-type precatalyst containing a bidentate ligand during alkene metathesis. Molecular simulation, 34(10-15):997-1012. [http://dx.doi.org/10.1080/08927020802411737]en
dc.identifier.issn1029-0435
dc.identifier.issn0892-7022 (Online)
dc.identifier.urihttp://hdl.handle.net/10394/3001
dc.identifier.urihttp://dx.doi.org/10.1080/08927020802411737
dc.identifier.urihttp://www.tandfonline.com/doi/abs/10.1080/08927020802411737
dc.description.abstractUsing density functional theory, the metathesis reaction of 1-octene in the presence of a Grubbs-type ruthenium alkylidene complex bearing a chelating pyridinyl alcoholate ligand, [RuCl(L)(O∧ N)( = CHPh)] (L = H2IMes or PCy3, O∧ N = 1-(2′-pyridinyl)cyclohexan-1-olate)), was investigated. The complete geometry optimisation and activation energy of various activation steps in the dissociative mechanism were performed at the GGA-PW91/DNP level of theory using Accelrys Materials Studio® 4.0. Two possible precatalyst initiations were explored, i.e. the dissociation of the labile N-atom of the O∧ N-ligand as well as the dissociation of ligand L, due to the belief that ruthenium-catalysed metathesis reactions proceed through 14-electron intermediates. The formation of the catalytically active heptylidene species is kinetically favoured for both the first- and second-generation chelating complexes. The computational results are in agreement with the experimental results obtained with NMR for the second-generation system. The computational results suggest that both phosphine ligand dissociation and hemilability may play a role in the metathesis reaction with the first-generation system
dc.language.isoenen
dc.publisherTaylor & Francisen
dc.subjectDFT
dc.subjectAlkene metathesis
dc.subjectGrubbs-type precatalyst
dc.subjectHemilabile ligand
dc.titleA DFT computational study of phosphine ligand dissociation versus hemilability in a Grubbs-type precatalyst containing a bidentate ligand during alkene metathesisen
dc.typeArticleen
dc.contributor.researchID10063552 - Vosloo, Hermanus Cornelius Moolman
dc.contributor.researchID11285214 - Jordaan, Margaritha


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