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dc.contributor.authorHow, Rebecca C.
dc.contributor.authorDingwall, Paul
dc.contributor.authorHembre, Robert T.
dc.contributor.authorPonasik, James A.
dc.contributor.authorTolleson, Ginette S.
dc.contributor.authorClarke, Matthew L.
dc.identifier.citationHow , R C , Dingwall , P , Hembre , R T , Ponasik , J A , Tolleson , G S & Clarke , M L 2017 , ' Composition of catalyst resting states of hydroformylation catalysts derived from bulky mono-phosphorus ligands, rhodium dicarbonyl acetylacetonate and syngas ' , Molecular Catalysis , vol. 434 , pp. 116-122 .
dc.identifier.otherPURE: 249064060
dc.identifier.otherPURE UUID: e417fc8a-fe99-4711-8394-b0b0b1b297cc
dc.identifier.otherScopus: 85029645249
dc.identifier.otherORCID: /0000-0002-2444-1244/work/59464612
dc.identifier.otherWOS: 000401676000014
dc.descriptionWe thank the Eastman Chemical Company for funding of RCH, EPSRC for funding of PD (EP003868/1).en
dc.description.abstractThe paper describes the composition of the resting states of several catalysts for alkene hydroformylation derived from bulky monophosphorus ligands. The results presented assess how bulky ligands compete with CO for the rhodium, and hence the role of ‘unmodified’ catalysts in alkene hydroformylation in the presence of these ligands. High Pressure Infra-Red (HPIR) spectroscopy was carried out at the rhodium and syngas concentrations typically used during catalysis experiments. These HPIR studies revealed that two ligands previously studied in Rh-catalysed hydroformylation react with [Rh(acac)(CO)2] and H2/CO to give the unmodified rhodium cluster, [Rh6(CO)16], as the only detectable species. Both less bulky phosphoramidites, and 1,3,5,7-Tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane, on the other hand, do not show the presence of [Rh6(CO)16], and hence catalysis proceeds by purely ligand modified species under normal conditions. In the case of the Rh/ phosphaadamantane catalysts, anecdotal evidence that this only forms a particularly useful catalyst above a certain pressure threshold can be understood in terms of how the catalyst composition varies with pressure. The ligands discussed have all been assessed in the hydroformylation of propene to separate their innate branched selectivity from their ability to isomerise higher alkenes to internal isomers.
dc.relation.ispartofMolecular Catalysisen
dc.rights© 2017 Elsevier B.V. All rights reserved. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at
dc.subjectUnmodified catalystsen
dc.subjectIn situ monitoringen
dc.subjectIR spectroscopyen
dc.subjectQD Chemistryen
dc.titleComposition of catalyst resting states of hydroformylation catalysts derived from bulky mono-phosphorus ligands, rhodium dicarbonyl acetylacetonate and syngasen
dc.typeJournal articleen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.description.statusPeer revieweden

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