TY - JOUR AB - 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. AU - Tay,DWP AU - Nobbs,JD AU - Romain,C AU - White,AJP AU - Aitipamula,S AU - van,Meurs M AU - Britovsek,GJP DO - 10.1021/acscatal.9b03007 EP - 671 PY - 2020/// SN - 2155-5435 SP - 663 TI - gem-dialkyl effect in diphosphine Ligands: synthesis, coordination behavior, and application in Pd-catalyzed hydroformylation T2 - ACS Catalysis UR - http://dx.doi.org/10.1021/acscatal.9b03007 UR - http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000506725100071&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202 UR - https://pubs.acs.org/doi/10.1021/acscatal.9b03007 UR - http://hdl.handle.net/10044/1/77358 VL - 10 ER -