Understanding Rh-catalysed Hydroformylation with Phosphite Ligands through Catalyst Speciation Analysis by Operando FlowNMR Spectroscopy

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

8 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.

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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