To examine the ligand exchange ability of the acetylide ligands, a model experiment was conducted by adding deb-H2 and triethylamine to 20•(Cl -)3 (Fig. , Fig. )). As observed in Fig. , the mass spectrum of the product featured peaks corresponding to [Au13(dppe)5(PA)2-x(deb-H)x] 3+ . This indicates that ligand exchange reactions occur even between acetylide ligands, and that ligand exchange reactions involving halogens or acetylides on the Au13 cluster are reversible, similarly to thiol or thiolate exchange reactions in thiolate-protected Au clusters such as Au25(SR)18. Therefore, control over the reaction and selective formation of the desired linkage structure is difficult using bridging ligands such as deb-H2. By contrast, the approach using the aforementioned complexation and end-cap ligands is a more straightforward and precise synthetic approach.