Irradiation of the Keggin-type [PW11O39{Ru(NO)}]4− (Ru-NO) polyoxometalate in CH3CN results in rapid NO ligand elimination with the formation of [PW11O39{RuIII(CH3CN)}]4− (Ru-CH3CN). This complex offers an easy entry into the Ru-based chemistry of the {PW11Ru} complex. Attempts to substitute N3− for CH3CN in the presence of an NaN3 excess lead a variety of products: (i) [PW11O39{RuIII(N3)}]4− (Ru-N3); (ii) [PW11O39{RuIII(N4HC-CH3)}]4− (Ru-Tz) as a click-reaction product; and (iii) [PW11O39{RuII(N2)}]5− (Ru-N2). UV-VIS, CV, and HR-ESI-MS techniques were used for the reaction monitoring and characterization of the products.
