Gold(III) adducts of 2-vinyl- and 2-ethylpyridine and cyclometallated derivatives of 2-vinylpyridine: Crystal structure of the cyclometallated derivative [Au(k2-C,N-CH2CH(Cl)-C5H4N)(PPh3)Cl][PF6]

Reaction of Na[AuCl(4)] with 2-vinylpyridine (vinpy) and 2-ethylpyridine (etpy) affords the N-bonded adducts Au(Rpy)Cl(3) (R = CH(2)=CH, vinpy; CH(3)CH(2), etpy). Cationic adducts, [Au(vinpy)(2)Cl][X](2) (X = BF(4), PF(6)) and [Au(etpy)(2)Cl(2)][BF(4)], were also obtained by reaction of Au(Rpy)Cl(3) with Rpy (1:1) and excess NaBF(4) or KPF(6). Thermal activation of Au(vinpy)Cl(3) in water gives the five-membered cycloaurated derivative [Au(k(2)-C,N-CH(2)CH(Cl)-C(5)H(4)N)Cl(2)] formally resulting through a trans nucleophilic addition of a chloride onto the C=C bond. No cyclometallated derivatives are obtained by reactions of Au(etpy)Cl(3). An X-ray crystal structure determination on the PPh(3) derivative [Au(k(2)-C,N-CH(2)CH(Cl)-C(5)H(4)N)(PPh(3))Cl] [PF(6)] was carried out. (C) 2009 Elsevier B.V. All rights reserved.