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)(12)Fe]X (X = Cl, Br, SO3CF3) comprised of a hexanuclear Lindqvist (M6O19n-) core. By substituting a V=O moiety from the well-defined hexavanadate clusters [V-n(IV) (V6-nO7)-O-V(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 H-1 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).