Easy Ligand Activation in the Coordination Sphere of Ru inside the [PW(11)O(39)](7–) Backbone

Irradiation of the Keggin-type [PW(11)O(39){Ru(NO)}](4−) (Ru-NO) polyoxometalate in CH(3)CN results in rapid NO ligand elimination with the formation of [PW(11)O(39){Ru(III)(CH(3)CN)}](4−) (Ru-CH(3)CN). This complex offers an easy entry into the Ru-based chemistry of the {PW(11)Ru} complex. Attempts to substitute N(3)(−) for CH(3)CN in the presence of an NaN(3) excess lead a variety of products: (i) [PW(11)O(39){Ru(III)(N(3))}](4−) (Ru-N(3)); (ii) [PW(11)O(39){Ru(III)(N(4)HC-CH(3))}](4−) (Ru-Tz) as a click-reaction product; and (iii) [PW(11)O(39){Ru(II)(N(2))}](5−) (Ru-N(2)). UV-VIS, CV, and HR-ESI-MS techniques were used for the reaction monitoring and characterization of the products.