12 Citations (SciVal)

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 languageEnglish
Article numbere202201204
JournalChemCatChem
Volume15
Issue number4
Early online date10 Jan 2023
DOIs
Publication statusPublished - 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

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