Multi-Nuclear, High-pressure, Operando FlowNMR Spectroscopic Study of Rh/PPh3 - Catalysed Hydroformylation of 1-Hexene

Alejandro Bara-Estaun, Catherine Lyall, John P Lowe, Paul G. Pringle, Paul Kamer, Robert Franke, Ulrich Hintermair

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17 Citations (SciVal)

Abstract

The hydroformylation of 1-hexene with 12 bar of 1:1 H2/CO in the presence of the catalytic system [Rh(acac)(CO)2]/PPh3 was successfully studied by real-time multinuclear high-resolution FlowNMR spectroscopy at 50 °C. Quantitative reaction progress curves that yield rates as well chemo- and regioselectivities have been obtained with varying P/Rh loadings. Dissolved H2 can be monitored in solution to ensure true operando conditions without gas limitation. 31P{1H} and selective excitation 1H pulse sequences were periodically interleaved with 1H FlowNMR measurements to correlate the reaction progress with Rh-phosphine intermediates. Stopped-flow experiments in combination with diffusion measurements and 2D heteronuclear correlation experiments showed the known tris-phosphine complex [RhH(CO)(PPh3)3] to generate rapidly exchanging isomers of the bis-phosphine complex [Rh(CO)2(PPh3)2] under CO pressure that directly enter the catalytic cycle. A mono-phosphine acyl complex has been identified as a late stage in-cycle reaction intermediate.
Original languageEnglish
Pages (from-to)422-442
JournalFaraday Discussions
Volume229
Early online date26 Mar 2020
DOIs
Publication statusPublished - 1 May 2021

Funding

This work was supported by the Royal Society (UF160458; fellowship to UH), the EPSRC Dynamic Reaction Monitoring Facility (EP/P001475/1), and the EPSRC Centre for Doctoral Training in Catalysis (EP/L016443; studentship to ABE). The authors thank Dr Christopher Kubis (LIKAT, Germany) for useful discussions and help with pump congurations.

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