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In situspectroscopic investigations on BiPhePhos modified rhodium complexes in alkene hydroformylationElectronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d4cy00481g
- Source :
- Catalysis Science & Technology; 2024, Vol. 14 Issue: 14 p3966-3983, 18p
- Publication Year :
- 2024
-
Abstract
- Structural and dynamic properties of BiPhePhos modified rhodium complexes under hydroformylation conditions have been investigated in detail by using high-pressure (HP) in situtransmission IR- and NMR-spectroscopy. An experiment design approach which combines component/reagent perturbations, in situ-FTIR measurements and chemometric peak group analysis (PGA) led to the identification of most relevant components. The ligand coordination in the structures of the hydrido and acyl 18-VE resting state complexes has been elucidated. The hydrido complex of the type e,e-[HRh(CO)2(P∩P)] represents the dominant resting state after catalyst preformation and during the n-regioselective hydroformylation. Dimer formation only takes place to a minor extent under severe reaction conditions under hydrogen depletion. Mono- and dinuclear hydrido monocarbonyl complexes are formed at higher ligand-to-metal ratios and low partial pressures of carbon monoxide. Both stereoisomeric forms of the bisphosphite modified acyl complexes e,a-[RC(O)Rh(CO)2(P∩P)] and e,e-[RC(O)Rh(CO)2(P∩P)] are generated as an equilibrium mixture.
Details
- Language :
- English
- ISSN :
- 20444753 and 20444761
- Volume :
- 14
- Issue :
- 14
- Database :
- Supplemental Index
- Journal :
- Catalysis Science & Technology
- Publication Type :
- Periodical
- Accession number :
- ejs66914578
- Full Text :
- https://doi.org/10.1039/d4cy00481g