The reaction of a series of 6-substituted-2,2'-bipyridines HL (N2C10H7R, R = CH,Ph, CHMePh, CMe,Ph, CH,Me, CMe, or CH,CMe,) with HAuC1, or Na[AuCl,] has been investigated. Under different experimental conditions, salts [H,L][AuCI,], adducts [Au(HL)Cl,] or cyclometallated derivatives [Au(L)Cl]m] (X = AuCl,, BF4 or PF,) have been isolated. The cyclometallated species arise from direct activation of a C-H bond either of a phenyl or a methyl substituent. The structures of an adduct [Au{N,CloH7(CHMePh)-6}C13] and two metallated species [Au{N,C,oH7(CMe,C,H,)-6}Cl][AuCl,] and [Au{N2CloH7(CMe2CH2)-