Pyridine-derived N-heterocyclic carbenes: An experimental and theoretical evaluation of the bonding in and reactivity of selected normal and abnormal complexes of Ni(II) and Pd(II)

DSpace/Manakin Repository

Show simple item record

dc.contributor.author Stander-Gobler, Elzet
dc.contributor.author Schuster, Oliver
dc.contributor.author Cronje, Stephanie
dc.contributor.author Tosh, Evangeline
dc.contributor.author Albrecht, Martin
dc.contributor.author Frenking, Gernot
dc.contributor.author Raubenheimer, Helgard G.
dc.contributor.author Heydenrych, Greta
dc.date.accessioned 2012-11-02T15:25:02Z
dc.date.available 2012-11-02T15:25:02Z
dc.date.copyright 2010 American Chemical Society en
dc.date.issued 2010-10-22
dc.identifier.citation Organometallics en
dc.identifier.uri http://hdl.handle.net/10197/3880
dc.description.abstract We report a thorough investigation of a series of isomeric complexes with the general formula trans-(pyridylidene)M(PPh3)2Cl (M = Pd, Ni). For the first time, a systematic comparison of normal, abnormal and remote bonding modes is presented. X-ray structural and 13C NMR data indicate the importance of carbenoid mesomeric contributions in their compound class. The catalytic performance of the palladium complexes, trans-(pyridylidene)Pd(PPh3)2Cl, as precursors in Suzuki-Miyaura-type cross-coupling suggests a correlation of remote bonding with catalyst robustness and thus effectivity. When metal precursors M(PPh3)4 are reacted with 2,4-dichloro pyridinium salts, preferential formation of remote carbene complexes occurs and indications are that electronic parameters rather than steric influences are responsible for the observed selectivity. Calculations at the BP86/TZ2P level of theory support interpretation of the results. en
dc.description.sponsorship Other funder en
dc.language.iso en en
dc.publisher ACS en
dc.subject Palladium en
dc.subject Pyridylidene en
dc.subject Normal carbene en
dc.subject Abnormal carbene en
dc.subject Nickel en
dc.subject.lcsh Palladium en
dc.subject.lcsh Organometallic compounds en
dc.subject.lcsh Carbenes (Methylene compounds) en
dc.subject.lcsh Nickel en
dc.title Pyridine-derived N-heterocyclic carbenes: An experimental and theoretical evaluation of the bonding in and reactivity of selected normal and abnormal complexes of Ni(II) and Pd(II) en
dc.type Journal Article en
dc.internal.availability Full text available en
dc.status Peer reviewed en
dc.identifier.volume 29 en
dc.identifier.issue 22 en
dc.identifier.startpage 5821 en
dc.identifier.endpage 5833 en
dc.identifier.doi 10.1021/om100431u
dc.neeo.contributor Stander-Gobler|Elzet|aut|
dc.neeo.contributor Schuster|Oliver|aut|
dc.neeo.contributor Cronje|Stephanie|aut|
dc.neeo.contributor Tosh|Evangeline|aut|
dc.neeo.contributor Albrecht|Martin|aut|
dc.neeo.contributor Frenking|Gernot|aut|
dc.neeo.contributor Raubenheimer|Helgard G.|aut|
dc.neeo.contributor Heydenrych|Greta|aut|
dc.description.othersponsorship South African National Research Foundation Alexander von Humboldt Foundation Alfred Werner Foundation Deutscher Akademischer Austauschdienst (DAAD) en
dc.description.admin DG 17/10/2012 en


Files in this item

This item appears in the following Collection(s)

Show simple item record

This item is available under the Attribution-NonCommercial-NoDerivs 3.0 Ireland. No item may be reproduced for commercial purposes. For other possible restrictions on use please refer to the publisher's URL where this is made available, or to notes contained in the item itself. Other terms may apply.

If you are a publisher or author and have copyright concerns for any item, please email research.repository@ucd.ie and the item will be withdrawn immediately. The author or person responsible for depositing the article will be contacted within one business day.

Search Research Repository


Advanced Search

Browse