gem-Dialkyl Effect in Diphosphine Ligands: Synthesis, Coordination Behavior, and Application in Pd-Catalyzed Hydroformylation
| Autor: | Charles Romain, James D. Nobbs, Andrew J. P. White, Srinivasulu Aitipamula, Martin van Meurs, George J. P. Britovsek, Dillon W. P. Tay |
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| Rok vydání: | 2019 |
| Předmět: |
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 |
| Zdroj: | ACS Catalysis. 10:663-671 |
| ISSN: | 2155-5435 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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