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

doi:10.1039/d2cy00312k

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 journal › Article › peer-review

9 Citations (SciVal)

Abstract

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 language	English
Pages (from-to)	5501-5516
Number of pages	16
Journal	Catalysis Science and Technology
Volume	12
Issue number	18
Early online date	26 Jul 2022
DOIs	https://doi.org/10.1039/d2cy00312k
Publication status	Published - 21 Sept 2022

Bibliographical note

Funding Information:
This work was supported by the Royal Society (UF160458; fellowship to UH), the EPSRC Dynamic Reaction Monitoring Facility at the University of Bath (EP/P001475/1), and the EPSRC Centre for Doctoral Training in Catalysis (EP/L016443; studentship to ABE).

Funding

This work was supported by the Royal Society (UF160458; fellowship to UH), the EPSRC Dynamic Reaction Monitoring Facility at the University of Bath (EP/P001475/1), and the EPSRC Centre for Doctoral Training in Catalysis (EP/L016443; studentship to ABE).

ASJC Scopus subject areas

Catalysis

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10.1039/d2cy00312kLicence: CC BY

Cite this

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

abstract = "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.",

author = "Alejandro Bara-Esta{\'u}n and Lyall, {Catherine L.} and Lowe, {John P.} and Pringle, {Paul G.} and Kamer, {Paul C.J.} and Robert Franke and Ulrich Hintermair",

note = "Funding Information: This work was supported by the Royal Society (UF160458; fellowship to UH), the EPSRC Dynamic Reaction Monitoring Facility at the University of Bath (EP/P001475/1), and the EPSRC Centre for Doctoral Training in Catalysis (EP/L016443; studentship to ABE). ",

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doi = "10.1039/d2cy00312k",

language = "English",

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AU - Bara-Estaún, Alejandro

AU - Lyall, Catherine L.

AU - Lowe, John P.

AU - Pringle, Paul G.

AU - Kamer, Paul C.J.

AU - Franke, Robert

AU - Hintermair, Ulrich

N1 - Funding Information: This work was supported by the Royal Society (UF160458; fellowship to UH), the EPSRC Dynamic Reaction Monitoring Facility at the University of Bath (EP/P001475/1), and the EPSRC Centre for Doctoral Training in Catalysis (EP/L016443; studentship to ABE).

PY - 2022/9/21

Y1 - 2022/9/21

N2 - 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.

AB - 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.

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DO - 10.1039/d2cy00312k

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ER -

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

Abstract

Bibliographical note

Funding

ASJC Scopus subject areas

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An Integrated, Multi-Dimensional In-Operando Reaction Monitoring Facility for Homogenous Catalysis Research

Cite this

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

Abstract

Bibliographical note

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Projects

An Integrated, Multi-Dimensional In-Operando Reaction Monitoring Facility for Homogenous Catalysis Research

Cite this

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