Functionalization of Heteropolyanions—Osmium and Rhenium Nitrido Derivatives of Keggin‐ and Dawson‐Type Polyoxotungstates: Synthesis, Characterization and Multinuclear ( 183 W, 15 N) NMR, EPR, IR, and UV/Vis Fingerprints

Reaction of K 10 [α 2 ‐P 2 W 17 O 61 ] or K 10 [α 1 ‐P 2 W 17 O 61 ] or [Bu 4 N][OsCl 4 N] in a water/methanol mixture, and subsequent precipitation with (Bu 4 N)Br provided [α 2 ‐P 2 W 17 O 61 {Os VI N}] 7− and [α 1 ‐P 2 W 17 O 61 {Os VI N}] 7− Dawson structures as tetrabutylammonium salts. Reactions of [(Bu 4 N) 4 ][α‐H 3 PW 11 O 39 ] with either [ReCl 3 (N 2 Ph 2 )(PPh 3 ) 2 ] or [Bu 4 N][ReCl 4 N] are alternatives to the synthesis of [(Bu 4 N) 4 ][α‐PW 11 O 39 {Re VI N}]. 183 W and 15 N NMR, EPR, IR, and UV‐visible spectroscopies and cyclic voltammetry have been used to characterize these compounds and the corresponding [(Bu 4 N) 4 ][α‐PW 11 O 39 {Os VI N}] Keggin derivative.