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)
|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
Raubenheimer, Helgard G.
|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
Carbenes (Methylene compounds)
|DOI:||10.1021/om100431u||Language:||en||Status of Item:||Peer reviewed|
|Appears in Collections:||Chemistry Research Collection|
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