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), [RPMo^V₆O₁₅(OH)₃{AsO₂(CH₃)₂}₃]²⁻ (R = H, HO, CH₃, HO₂CCH₂, HO₂CC₂H₄, C₆H₅, 4-FC₆H₄, 4-F₃COC₆H₄) and the monoanionic mixed-valent heptamolybdate [HOMo^VIMo^V₆O₁₅(OH)₃{AsO₂(CH₃)₂}₃]⁻. These nine novel polyanions feature a reduced, cyclic hexanuclear {Mo^V₆O₂₄} 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.