A first structural and theoretical comparison of pyridinylidene-type rNHC (remote N-heterocyclic carbene) and NHC complexes of Ni(II) obtained by oxidative substitution

Schneider S.K. ; Julius G.R. ; Loschen C. ; Raubenheimer H.G. ; Frenking G. ; Herrmann W.A. (2006)


A series of cationic pyridinylidene and quinolinylidene complexes of chlorobis(triphenylphosphine)nickel(ii) were prepared by oxidative substitution of Ni(PPh3)4 with methylated chloropyridines or chloroquinolines. NMR as well as X-ray crystallographic studies confirmed the trans arrangement of the two phosphines in the products. Calculations, using suitable model compounds at the BP86/TZVP level, clearly differentiate between a standard imidazolylidene complex and new complexes of the NHC-type on the one hand, and new complexes classified as rNHC-types - with the heteroatom distant from the carbene carbon - on the other. The latter form significantly stronger bonds - mainly of an electrostatic nature - with the metal. © The Royal Society of Chemistry 2006.

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