Easy Ligand Activation in the Coordination Sphere of Ru inside the [PWO] Backbone.

Irradiation of the Keggin-type [PWO{Ru(NO)}] () polyoxometalate in CHCN results in rapid NO ligand elimination with the formation of [PWO{Ru(CHCN)}] (). This complex offers an easy entry into the Ru-based chemistry of the {PWRu} complex. Attempts to substitute N for CHCN in the presence of an NaN excess lead a variety of products: (i) [PWO{Ru(N)}] (); (ii) [PWO{Ru(NHC-CH)}] () as a click-reaction product; and (iii) [PWO{Ru(N)}] (). UV-VIS, CV, and HR-ESI-MS techniques were used for the reaction monitoring and characterization of the products.