Exploring the potential energy surface for interaction of a trichloro(diethylenetriamine)gold(III) complex with strong nucleophiles

► Reactivity of gold(III) complexes are modeled. ► Direct substitution reaction and ring-opening are addressed. ► The kinetics follows the order: SCN− > N3− > H2O and the thermodynamics: N3− > SCN− > H2O. ► Ring-opening side reaction is kinetically important for SCN− and N3−.