Understanding a hydroformylation catalyst that produces bran

Michael dc.contributor.author Clarke， reaction of the rhodium-hydrido dicarbonyl with allylbenzene allowed further detailed spectroscopic characterization of four- and five-coordinate rhodium-acyl species. Under single-turnover conditions the ratios of branched to linear acyl species were preserved in the final ratios of aldehyde products. Theoretical investigations uncovered unexpected stabilizing CH-π interactions between the ligand and substrate which influenced the high branched selectivity by causing potentially low energy pathways to become unproductive. Energy span and degree of TOF control analysis strongly support experimental observations and mechanistic rationale. A three-dimensional quadrant model was built to represent the structural origins of regio- and enantioselectivity. dc.format.extent 5142219 dc.language.iso eng dc.relation.ispartof Journal of the American Chemical Society en dc.rights Copyright 2017 American Chemical Society. This work has been made available online in accordance with the publishers policies. This is the author created accepted version manuscript following peer review and as such may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1021/jacs.7b09164 en dc.subject QD Chemistry en dc.subject DAS en dc.subject BDC en dc.subject R2C en dc.subject.lcc QD en dc.title Understanding a hydroformylation catalyst that produces branched aldehydes from alkyl alkenes en dc.type Journal article en dc.contributor.sponsor EPSRC en dc.contributor.institution University of St Andrews.School of Chemistry en dc.contributor.institution University of St Andrews.EaSTCHEM en dc.identifier.doi 10.1021/jacs.7b09164 dc.description.status Peer reviewed en dc.date.embargoedUntil 2018-10-25 dc.identifier.url en dc.identifier.url https://www.scopus.com/pages/publications/85033220139 en dc.identifier.grantnumber EP/M003868/1 en ， Alexandra Martha Zoya dc.contributor.author Buehl， J A， Buehl， Slawin， Luke dc.contributor.author Slawin， Crawford， Fuentes， pp. 1592115932. https://doi.org/10.1021/jacs.7b09164 en dc.identifier.issn 0002-7863 dc.identifier.other ORCID: /0000-0002-1095-7143/work/48131743 dc.identifier.other ORCID: /0000-0002-9527-6418/work/56861737 dc.identifier.other ORCID: /0000-0002-2444-1244/work/59464622 dc.identifier.uri https://hdl.handle.net/10023/16318 dc.description The authors thank the EPSRC for funding (EP/M003868/1). en dc.description.abstract This paper reports experimental and computational studies on the mechanism of a rhodium-catalysed hydroformylation that is selective for branched aldehyde products from unbiased alkene substrates. This highly unusual selectivity relies on a phospholane-phosphite ligand prosaically called BOBPHOS. Kinetic studies using in situ high pressure IR (HPIR) and the reaction progress kinetic analysis methodology suggested two steps in the catalytic cycle were involved as turnover determining. Negative order in CO and positive orders in alkene and H2 were found and the effect of hydrogen and carbon monoxide partial pressures on selectivity were measured. Labeling studies found rhodium hydride addition to the alkene to be largely irreversible. Detailed spectroscopic HPIR and NMR characterization of activated rhodium-hydrido dicarbonyl species were carried out. In the absence of H2， Jos A. dc.contributor.author Crawford， vol. 139， Paul dc.contributor.author Fuentes， 'Understanding a hydroformylation catalyst that produces branched aldehydes from alkyl alkenes'， L， M L 2017， Journal of the American Chemical Society， P， Matthew L dc.date.accessioned 2018-10-24T23:50:08Z dc.date.available 2018-10-24T23:50:08Z dc.date.issued 2017-11-08 dc.identifier 251350605 dc.identifier f4931072-3b63-4e1a-b262-d06ccfbab29b dc.identifier 85033220139 dc.identifier 000415028200054 dc.identifier.citation Dingwall， dc.contributor.author Dingwall， M Clarke， no. 44， A M Z，。