Thiolate protected gold nanoclusters have gained substantial attention due to their atomically precise compositions and well-defined structures. Recent discoveries have shed the light on the dynamic nature of clusters and their reactivity leading to the formation of heterometallic clusters with interesting properties. In this thesis we investigate the reactivity of Au25(SR)18 and Au38(SR)24 nanoclusters by exploring new alloying methods, their mechanism, and the properties of the formed alloys. Using the known cluster - metal thiolate alloying reaction, the first copper adduct (Cu1Au38) was synthesized and its isomers were separated. Through the reaction of clusters with different metal foils a new doping technique was introduced, and the thiol ligand's importance in the reaction was exposed. Additionally, the intercluster reaction of Au25 with Ag25 nanocluster was controlled for the first time unravelling a two-phase mechanism. Finally, the reactivity of Au25 with Ag nanoparticles was explored and introduced as a new doping method.