Title
Oxidative addition of haloheteroarenes to palladium(0) : concerted versus <tex>$S_{N}AR$</tex>-type mechanism Oxidative addition of haloheteroarenes to palladium(0) : concerted versus <tex>$S_{N}AR$</tex>-type mechanism
Author
Faculty/Department
Faculty of Sciences. Chemistry
Publication type
article
Publication
Weinheim ,
Subject
Chemistry
Source (journal)
Chemistry: a European journal. - Weinheim
Volume/pages
21(2015) :21 , p. 7858-7865
ISSN
0947-6539
ISI
000354204300031
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
The kinetics of the oxidative additions of haloheteroarenes HetX (X=I, Br, Cl) to [Pd0(PPh3)2] (generated from [Pd0(PPh3)4]) have been investigated in THF and DMF and the rate constants have been determined. In contrast to the generally accepted concerted mechanism, Hammett plots obtained for substituted 2-halopyridines and solvent effects reveal a reaction mechanism dependent on the halide X of HetX: an unprecedented SNAr-type mechanism for X=Br or Cl and a classical concerted mechanism for X=I. These results are supported by DFT studies.
E-info
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000354204300031&DestLinkType=RelatedRecords&DestApp=ALL_WOS&UsrCustomerID=ef845e08c439e550330acc77c7d2d848
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000354204300031&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=ef845e08c439e550330acc77c7d2d848
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000354204300031&DestLinkType=CitingArticles&DestApp=ALL_WOS&UsrCustomerID=ef845e08c439e550330acc77c7d2d848
Handle