gem-dialkyl effect in diphosphine Ligands: synthesis, coordination behavior, and application in Pd-catalyzed hydroformylation

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Title: gem-dialkyl effect in diphosphine Ligands: synthesis, coordination behavior, and application in Pd-catalyzed hydroformylation
Authors: Tay, DWP
Nobbs, JD
Romain, C
White, AJP
Aitipamula, S
Van Meurs, M
Britovsek, GJP
Item Type: Journal Article
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.
Issue Date: 3-Jan-2020
Date of Acceptance: 1-Dec-2019
URI: http://hdl.handle.net/10044/1/77358
DOI: 10.1021/acscatal.9b03007
ISSN: 2155-5435
Publisher: American Chemical Society
Start Page: 663
End Page: 671
Journal / Book Title: ACS Catalysis
Volume: 10
Issue: 1
Copyright Statement: © 2019 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acscatal.9b03007
Keywords: Science & Technology
Physical Sciences
Chemistry, Physical
Chemistry
Thorpe-Ingold
hydroformylation
gem-dialkyl
chelate
bidentate
diphosphine
BITE-ANGLE
PHOSPHORUS LIGANDS
CYCLIC SULFATES
METAL-CATALYSTS
BASIS-SETS
ISOMERIZATION
COMPLEXES
Science & Technology
Physical Sciences
Chemistry, Physical
Chemistry
Thorpe-Ingold
hydroformylation
gem-dialkyl
chelate
bidentate
diphosphine
BITE-ANGLE
PHOSPHORUS LIGANDS
CYCLIC SULFATES
METAL-CATALYSTS
BASIS-SETS
ISOMERIZATION
COMPLEXES
0302 Inorganic Chemistry
0305 Organic Chemistry
0904 Chemical Engineering
Publication Status: Published
Embargo Date: 2020-12-03
Online Publication Date: 2019-12-03
Appears in Collections:Chemistry
Catalysis and Advanced Materials
Faculty of Natural Sciences
Grantham Institute for Climate Change