Room-temperature cyclometallation of amines, imines and oxazolines with [MCl2Cp*]2(M = Rh, Ir) and [RuCl2(p-cymene)]2

N,N-Dimethylbenzylamine, alkyl and aryl imines derived from benzaldehyde, and 2-phenyl-4,4-dimethyloxazoline all undergo cyclometallation with [IrCl2Cp*]2 (Cp* = η-C5Me5) when treated with NaOAc in dichloromethane at room temperature. The imines are also cyclometallated by [RhCl2Cp*]2 under the same conditions whilst only N-alkyl imines are cyclometallated by [RuCl2(p-cymene)]2. The role of acetate in the cyclometallation is more than just as a base. X-Ray structures of cyclometallated complexes [MCl{C6H4-2-C(H)NCH2CH2OMe-κC,N}(η-ring)](M = Ir, Rh ring = Cp*; M = Ru, ring = p-cymene), [MCl{C6H4-2-C(H)NCH2CH2OMe-κC,N}Cp*](M = Ir, Rh), [RuCl(η2-O2CMe)(p-cymene)] and [IrCl2(NH2Ph)Cp*] are reported.