Please use this identifier to cite or link to this item:
|Title:||Aryl Fluoride Reductive Elimination from PdII Complexes: A Descriptor to Guide Ligand Selection||Authors:||Cui, L.
|Issue Date:||14-Jun-2011||Citation:||Cui, L., Saeys, M. (2011-06-14). Aryl Fluoride Reductive Elimination from PdII Complexes: A Descriptor to Guide Ligand Selection. ChemCatChem 3 (6) : 1060-1064. ScholarBank@NUS Repository. https://doi.org/10.1002/cctc.201000461||Abstract:||The effect of ligand selection on the reductive elimination barrier of PdII aryl fluoride complexes was analyzed by using density functional theory (DFT) calculations. A separate Evans-Polanyi relationship between the activation barriers and the reaction energies is found for C, F reductive elimination from monodentate and bis(monodentate) PdII complexes. For comparable reaction energies, the reductive elimination barriers for monodentate complexes [LPd(Ar)F] (L=PR3, Ar=aryl) were calculated to be 80kJmol-1 lower than for bis(monodentate) complexes [L2Pd(Ar)F]. Natural population analysis demonstrated that the partial charges on the Pd center and on the aryl α-carbon can be used as a descriptor for the reductive elimination barriers. The presence of a trans phosphine ligand in bis(monodentate) complexes increases the Pd, C charge density and hence increases the C, F reductive elimination barrier. The importance of the Pd, C charge density can be understood by performing a natural bond orbital analysis. Indeed, C, F reductive elimination is best described as the nucleophilic attack of one of the fluorine lone pairs on the antibonding Pd, C orbital, and the energy difference between this fluorine lone pair and the antibonding Pd, C orbital determines the rate of this nucleophilic attack. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.||Source Title:||ChemCatChem||URI:||http://scholarbank.nus.edu.sg/handle/10635/88555||ISSN:||18673880||DOI:||10.1002/cctc.201000461|
|Appears in Collections:||Staff Publications|
Show full item record
Files in This Item:
There are no files associated with this item.
checked on Jan 29, 2023
WEB OF SCIENCETM
checked on Jan 20, 2023
checked on Jan 26, 2023
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.