Mapping catalyst activation, turnover speciation and deactivation in Rh/PPh3-catalysed olefin hydroformylation

Alejandro Bara-Estaún, Catherine L. Lyall, John P. Lowe, Paul G. Pringle, Paul C.J. Kamer, Robert Franke, Ulrich Hintermair

Research output: Contribution to journalArticlepeer-review

4 Citations (SciVal)


We report new insights into the fate of the precious metal during hydroformylation catalysis of 1-hexene with Rh/PPh3 complexes using multi-nuclear operando FlowNMR spectroscopy. By applying selectively excited 1H and 31P{1H} NMR pulse sequences we were able to characterise and quantify key hydrido-rhodium and acyl-rhodium intermediates formed during turnover as well as dormant dimeric carbonyl complexes. The quantitative catalyst distribution maps derived this way explain catalyst stability and activity across a range of reaction conditions, including why CO-lean conditions give faster hydroformylation catalysis through the suppression of dimer and cluster formation. The activation behaviour of five commonly used precursors and the thermal stability of the phosphine-hydrido complex [RhH(CO)(PPh3)3] have been investigated, and the benefits of applying controlled temperature gradients for quantitative FlowNMR spectroscopic reaction monitoring of dynamic catalyst systems are demonstrated.

Original languageEnglish
Pages (from-to)5501-5516
Number of pages16
JournalCatalysis Science and Technology
Issue number18
Early online date26 Jul 2022
Publication statusPublished - 21 Sept 2022

ASJC Scopus subject areas

  • Catalysis


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