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)

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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)
Authors: Stander-Gobler, Elzet
Schuster, Oliver
Cronje, Stephanie
Tosh, Evangeline
Albrecht, Martin
Frenking, Gernot
Raubenheimer, Helgard G.
Heydenrych, Greta
Permanent link: http://hdl.handle.net/10197/3880
Date: 22-Oct-2010
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.
Funding Details: Other funder
Type of material: Journal Article
Publisher: ACS
Copyright (published version): 2010 American Chemical Society
Keywords: Palladium;Pyridylidene;Normal carbene;Abnormal carbene;Nickel
Subject LCSH: Palladium
Organometallic compounds
Carbenes (Methylene compounds)
Nickel
DOI: 10.1021/om100431u
Language: en
Status of Item: Peer reviewed
Appears in Collections:Chemistry Research Collection

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