210362-41-7Relevant academic research and scientific papers
Novel palladium(II) allyl complexes with nitrogen-sulfur donor bidentate ligands. Mechanism of allyl animation of [Pd(η3-allyl)-(N-SR)]ClO4 (allyl = C3H5; N-SR = C5H4N-2-CH2SR, R = C6H5, C2H5) in the presence of activated olefins.
Canovese, Luciano,Visentin, Fabiano,Uguagliati, Paolo,Chessa, Gavino,Lucchini, Vittorio,Bandoli, Giuliano
, p. 385 - 394 (1998)
The reactions of [Pd(η3-C3H5) (C5H4N-2-CH2SR) ]+ (R = C6H5, C2H5) with amines in the presence of fumaronitrile (fn), involving the formation of allylamines, were studied kinetically in CHCl3 by UV-Vis techniques. The proposed stepwise mechanism involves a fast pre-equilibrium in which the mixed N-SR ligand is displaced by the amine, giving an inert bis-amino allyl species. The concomitant rate-determining bimolecular attack by the amine yields the allylamine and the corresponding Pd(0) complexes [Pd(η2-fn) (C5H4N-2-CH2SR)]. The solid state structure of complex [Pd(η3-C3H5)(C5H 4N-2-CH2SC6H5)]ClO4 was determined by X-ray crystallography. A preliminary 1H NMR study of the fluxional manifestations was carried out. The apparent rotation of the allyl moiety is operative at the lowest temperature. Increasing the temperature promotes the breaking and rearrangement of the Pd-S bond and, finally, the η3-η1-η3 rearrangement of the allyl fragment.
