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gem-Dialkyl Effect in Diphosphine Ligands: Synthesis, Coordination Behavior, and Application in Pd-Catalyzed Hydroformylation
- Source :
- ACS Catalysis. 10:663-671
- Publication Year :
- 2019
- Publisher :
- American Chemical Society (ACS), 2019.
-
Abstract
- A series of palladium complexes with C3-bridged bidentate bis(diphenylphosphino)propane ligands with substituents of varying steric bulk at the central carbon have been synthesized. The size of the gem-dialkyl substituents affects the C–C–C bond angles within the ligands and consequently the P–M–P ligand bite angles. A combination of solid-state X-ray diffraction (XRD) and density functional theory (DFT) studies has shown that an increase in substituent size results in a distortion of the 6-membered metal–ligand chair conformation toward a boat conformation, to avoid bond angle strain. The influence of the gem-dialkyl effect on the catalytic performance of the complexes in palladium-catalyzed hydroformylation of 1-octene has been investigated. While hydroformylation activity to nonanal decreases with increasing size of the gem-dialkyl substituents, a change in chemoselectivity toward nonanol via reductive hydroformylation is observed.
- Subjects :
- Steric effects
PHOSPHORUS LIGANDS
CYCLIC SULFATES
Denticity
BITE-ANGLE
0904 Chemical Engineering
chemistry.chemical_element
chelate
Bite angle
010402 general chemistry
0305 Organic Chemistry
01 natural sciences
Medicinal chemistry
Catalysis
bidentate
0302 Inorganic Chemistry
Chelation
hydroformylation
BASIS-SETS
ISOMERIZATION
Science & Technology
Chemistry, Physical
010405 organic chemistry
Chemistry
Thorpe-Ingold
METAL-CATALYSTS
General Chemistry
0104 chemical sciences
Physical Sciences
gem-dialkyl
COMPLEXES
diphosphine
Isomerization
Hydroformylation
Palladium
Subjects
Details
- ISSN :
- 21555435
- Volume :
- 10
- Database :
- OpenAIRE
- Journal :
- ACS Catalysis
- Accession number :
- edsair.doi.dedup.....f1727f829e72622868b1cc5388a0ab2a