Cinellu, Maria Agostina and Maiore, Laura and Minghetti, Giovanni and Stoccoro, Sergio and Zucca, Antonio and Manassero, Mario and Manassero, Carlo (2009) Gold(III) adducts with chiral pyridinyl-oxazolines: synthesis, reactivity of the coordinated ligands, and structural characterizations. Organometallics, Vol. 28 (24), p. 7015-7024. eISSN 1520-6041. Article.
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Novel gold(III) pyridinyl-oxazoline cationic complexes [Au(pyoxR)Cl2][X] [pyoxR = (S)-4-R-2-(pyridin-2-yl)-4,5-dihydrooxazole, with R = iPr, Bn, and (R)-4-phenyl-2-(pyridin-2-yl)-4,5-dihydrooxazole; X = PF6, AuCl4, or mixtures of the two anions] were synthesized and structurally characterized. Reaction of the adducts with NaOAc in aqueous solution afforded the neutral complexes [Au(N,N′,O)Cl] of the deprotonated ligands N-(1-hydroxy-3-R-2-yl)pyridine-2-carboxamide (R = iPr, Ph), N,N′H,OH, resulting from ring-opening of the bound pyox ligand by hydroxide ions and incorporation of hydroxide into the ring-opened products. Reaction of [Au(N,N′,O)Cl] (R = iPr) with HX (X = Cl, BF4, OTf) in aqueous solution resulted in protonation of the coordinated alkoxo group and its displacement from the coordination sphere to give the adducts [Au(N,N′,OH)ClX] (X = OTf, Cl) or the aquo complex [Au(N,N′,OH)(OH2)Cl]+ (X = BF4). Crystal structure characterizations were carried out on both [Au(N,N′,O)Cl] and [Au(N,N′,OH)Cl2] (R = iPr). Equimolar mixtures of the ring-opened derivative [Au(N,N′,O)Cl] (R = iPr) and either silver salts or HBF4 were found to promote, under mild conditions, polymerization of styrenes.
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