Self-Assembled, Iron-Functionalized Polyoxovanadate Alkoxide Clusters

Herein we report the synthesis of a series of iron-functionalized, mixed-valent, polyoxovanadate alkoxide clusters, [V5O6(OCH3)12Fe]X (X = Cl, Br, SO3CF3) comprised of a hexanuclear Lindqvist (M6O19(n-)) core. By substituting a V═O moiety from the well-defined hexavanadate clusters [V(IV)nV(V)6-nO7(OR)12](4-n) (R = Me, Et) with a metal cation, we have developed a novel template for investigation of the organometallic properties of these systems. Characterization of the clusters was performed by (1)H NMR, Fourier transform infrared, and electron absorption spectroscopies and electrospray ionization mass spectrometry. The IR and UV-vis spectra suggest substantial electronic delocalization, similar to the previously reported cluster, V6O7(OCH3)12.