Layered zirconium phosphate chloride dimethyl sulfoxide as a two-dimensional exchanger of anionic ligands. Part I. Substitution of chloride with inorganic monodentate ligands

Article abstract of DOI:10.1021/ic010643v

Crystalline ZrPO₄Cl(CH₃)₂SO was prepared by direct precipitation in the presence of oxalic acid as a zirconium complexing agent. The structure of ZrPO₄Cl(CH₃)₂SO, refined with the Rietveld method using X-ray powder diffraction data, was confirmed to be close to that of the compound prepared using γ-zirconium phosphate as a precursor. Chloride anions directly bonded to zirconium were found to act as weak ligands; this made possible their replacement with other monodentate anionic ligands. The preparation and a preliminary characterization of a series of inorganic derivatives obtained by topotactic replacement of Cl with OH, Br, MSO₄ (M= H, NH₄, Na), NaMoO₄, and HCrO₄ anions is reported. The possibility of replacement of chloride also with organic anions, such as alkoxides and carboxylates, and the possibility of substituting also dimethyl sulfoxide with other neutral ligands, as shown by preliminary study, makes ZrPO₄Cl(CH₃)₂SO a useful and very flexible precursor for materials chemistry.