Publication
Title
A DFT study of site-selectivity in oxidative addition reactions with $Pd^{0}$ complexes: the effect of an azine nitrogen and the use of different types of halogen atoms in the substrate
Author
Abstract
 The site-selectivity of Pd-catalyzed reactions of 2,3-dihalopyridines [2,3-dichloropyridine (1), 2,3-dibromopyridine (3) and 2-chloro-3-iodopyridine (2)] has been studied by computing the oxidative addition process using DFT calculations. The activating effect of the azine nitrogen atom on C(2) and C(3) has been obtained by comparison with the corresponding dihalobenzene [1,2-dichlorobenzene (4), 1,2-dibromobenzene (5) and 1-chloro-2-iodobenzene (6)]. The performed calculations involve the use of Pd(PPh3)2, Pd(BINAP) and Pd(XANTPHOS) as catalysts. The formation of pre-reactive complexes proved to be a very important factor in the determination of the activation energy values. A comparison with the simplified systems Pd(PPH3)2, Pd(H-BINAP) and Pd(HXANTPHOS) revealed that care has to be taken when simplified catalyst systems are used for the simulation of the oxidative addition process.
Language
English
Source (journal)
European journal of organic chemistry. - Weinheim
Publication
Weinheim : 2010
ISSN
1434-193X
Volume/pages
16(2010), p. 3152-3158
ISI
000278888700016
Full text (Publishers DOI)
Full text (publishers version - intranet only)
UAntwerpen
 Faculty/Department Research group Publication type Subject Affiliation Publications with a UAntwerp address