Composition of catalyst resting states of hydroformylation catalysts derived from bulky mono-phosphorus ligands, rhodium dicarbonyl acetylacetonate and syngas
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The 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.
How , 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 . https://doi.org/10.1016/j.mcat.2017.01.030
© 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 https://doi.org/10.1016/j.mcat.2017.01.030
DescriptionWe thank the Eastman Chemical Company for funding of RCH, EPSRC for funding of PD (EP003868/1).
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