Organophosphonate- and dimethylarsinate-functionalized hexamolybdates(V) and their solution and gas phase properties

Abstract

Here we report a comprehensive study on the synthesis and characterization of dimethylarsinate-functionalized phosphomolybdates(V), [RPMoV6O15(OH)3{AsO2(CH3)2}3]2- (R = H, HO, CH3, HO2CCH2, HO2CC2H4, C6H5, 4-FC6H4, 4-F3COC6H4) and the monoanionic mixed-valent heptamolybdate [HOMoVIMoV6O15(OH)3{AsO2(CH3)2}3]-.These nine novel polyanions feature a reduced, cyclic hexanuclear {MoV6O24} core, decorated peripherally by three dimethylarsinate ligands and centrally by six different organophosphonate groups including fluorinated ones, as well as phosphate and phosphite. The polyanions were synthesized under simple one-pot aqueous solution conditions and characterized (i) in the solid state by single-crystal and powder XRD, TGA, elemental analysis, (ii) in solution by multinuclear (1H, 31P, 19F, 13C) NMR, and (iii) in the gas phase by ESI mass spectrometry.