Reaction of triazolium precursors [MIC(CH2)n- H+]I− (n=1–3) with potassium hexamethyldisilazane (KHMDS) and AuCl(SMe2) generates the gold(I) complexes of the type MIC(CH2)n⋅AuI. Visible light exposure of the latter complexes promotes a spontaneous disproportionation process rendering gold(III) complexes of the type [{MIC(CH2)n}2⋅AuI2]+I−. Both the AuI and AuIII complex series were tested in the catalytic hydrohydrazination of terminal alkynes using hydrazine as nitrogen source.