Phenylimido Functionalization of alpha-[PW12O40]3-.
A synthetic route of potentially wide scope is reported herein for the organoimido functionalization of polyoxotungstates. This report focuses on the reaction between the monovacant lacunary polyoxotungstate, alpha-((n-C4H9)4N)4H3[PW11O39], and W(NC6H5)Cl4 in anhydrous acetonitrile. Evidence from 1H, 31P, 183W, and 1H-183W HMQC NMR spectroscopy, as well as cyclic voltammetry, electronic absorption, and elemental analysis, is presented for the formation of alpha-[PW12O39(NC6H5)]3- (2) of Cs symmetry, which is structurally related to Td alpha-[PW12O40]3- (3) by formal oxide substitution. The electronic structure of 2 is significantly perturbed from 3 with significant arylimido-->tungsten charge transfer, primarily localized to the W(NC6H5) fragment with secondary charge delocalization onto the remaining W and corner-shared bridging O atoms. This is consistent with the approximately 800 ppm downfield 183W NMR shift for the phenylimido-tungsten, modest cathodic shifts in reversible redox potentials, electronic and IR spectra, and density functional theory calculations.
Duhacek
Jeff C
JC
Department of Chemistry and Biochemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, USA.
Duncan
Dean C
DC