Functionalization of Polyoxometalates: From Lindqvist to Keggin Derivatives. 1. Synthesis, Solution Studies, and Spectroscopic and ESI Mass Spectrometry Characterization of the Rhenium Phenylimido Tungstophosphate [PW₁₁O₃₉{ReNC₆H₅}]^4-

Abstract

Reaction of [Bu(4)N](4)[H(3)PW(11)O(39)] with [Re(NPh)Cl(3)(PPh(3))(2)], in acetonitrile and in the presence of NEt(3), provided the first Keggin-type organoimido derivative [Bu(4)N](4)[PW(11)O(39)(ReNPh)] (Ph = C(6)H(5)) (1). The functionalization was clearly demonstrated by various techniques including (1)H and (14)N NMR, electrochemistry, and ESI mass spectrometry. Conditions for the formation of 1 are also discussed.