Projects per year
Abstract
Phosphites are industrially important ligands for the Rh-catalysed hydroformylation of olefins because they produce more active catalysts than phosphines, which is mainly due to their strong π-acceptor properties facilitating CO dissociation from the metal centre. Herein, the effect of three prominent phosphite ligands (triphenylphosphite, Alkanox and BiPhePhos) on catalyst speciation during turnover is investigated using multi-nuclear operando FlowNMR spectroscopy. The quantitative catalyst distribution maps derived explain activity trends across a range of catalytic reaction conditions that show how phosphites produce more active catalysts, including reduced formation of inactive Rh0 dimers in the absence of substrate during pre-activation and at the end of the reaction. Additionally, [(alkanox)Rh(acac)] complexes have been found to be of high stability which can be exploited for post-catalytic Rh recovery by simple addition of 2,4-pentanediones.
Original language | English |
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Article number | e202201204 |
Journal | ChemCatChem |
Volume | 15 |
Issue number | 4 |
Early online date | 10 Jan 2023 |
DOIs | |
Publication status | Published - 20 Feb 2023 |
Data Availability Statement
The data that support the findings of this study are available in the supplementary material of this article.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).
Keywords
- high-resolution FlowNMR spectroscopy
- hydroformylation
- mechanisms in homogeneous catalysis
- phosphite ligands
- rhodium complexes
ASJC Scopus subject areas
- Catalysis
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
Fingerprint
Dive into the research topics of 'Understanding Rh-catalysed Hydroformylation with Phosphite Ligands through Catalyst Speciation Analysis by Operando FlowNMR Spectroscopy'. Together they form a unique fingerprint.Projects
- 1 Finished
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An Integrated, Multi-Dimensional In-Operando Reaction Monitoring Facility for Homogenous Catalysis Research
Davidson, M. (PI), Hintermair, U. (CoI), Knight, J. (CoI), Lowe, J. (CoI), Lowe, J. (CoI) & Lubben, A. T. (CoI)
Engineering and Physical Sciences Research Council
10/07/16 → 9/07/19
Project: Research council
Equipment
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Avance III 500 MHz Nuclear Magnetic Resonance (NMR) Spectrometer (9West)
Material and Chemical Characterisation (MC2)Facility/equipment: Equipment