Anionic Ligand Exchange on ZrPO₄Cl(dmso):  Alkoxide and Carboxylate Derivatives

Abstract

This paper reports the preparation and characterization of a series of organic derivatives of ZrPO(4)Cl(CH(3))(2)SO obtained by topotactic anion exchange of chloride ligands with several n-alkoxide (RO) and carboxylate groups (RCOO). Exchange with alkoxides, with an alkyl chain length from 2 to 8 carbon atoms, gave products of general formula ZrPO(4)RO(CH(3))(2)SO. In these derivatives alkoxide groups, covalently bonded to zirconium atoms via Zr-O bonds, point toward the interlayer region. Carboxylate derivatives, of general formula ZrPO(4)[(RCOO)(CH(3))(2)SO](1)(-)(x)(OH H(2)O)(x), were obtained using benzoate (x = 0), nitrobenzoate (x = 0.3), and phenylacetate (x = 0.2) groups. The thermal behavior of these organic derivatives is discussed. Due to this reactivity, ZrPO(4)Cl(CH(3))(2)SO is an attractive precursor for materials chemistry.

Synthesis and characterization of substituted salicylate zirconium compounds and their catalytic activity over ε-caprolactone

“…Reactions of Zr(OPr) 4 with substituted salicylic acid in 1:1 molar ratio in 1-propanol at room temperature gave the product of (Cl-SA) 2 The formulations of complexes were based on the integration of 1 H-NMR spectra, mass measurements, TGA measurements, FT-IR data, and the amounts of hydrogen and carbon measured by elemental analysis. In the presence of salicylic acid derivatives, some of the alkoxy groups from the starting materials undergo condensation to form oxo group.…”

“…The complexing carboxylate ligands such as methacrylate, chloro acetate, 3-pentenoate, perfluoroheptanoate, butynoate, phthalate, pyridine-2-carboxylate or related ligands have often been reported in the literature as chemical additives to regulate the reactivity of zirconium alkoxides [1][2][3][4][5][6][7][8]. When some of the alkoxide groups are substituted by carboxylate groups, a new molecular precursor can be obtained which exhibits a different molecular structure and reactivity.…”

Phosphate-Based Organic-Inorganic Hybrid Materials: Design, Construction and Technological Applications

“…and neutral monodentate ligands (sulphoxides, amines, etc. ), respectively [45]. If dialkoxides or dicarboxylate ligands are used, λ-layered-pillared organic-inorganic derivatives are obtained.…”

“…These organic-inorganic frameworks are prepared by two main synthetic approaches: (i) thermal decomposition of zirconium fluoro-complex in the presence of phosphonic acids (α-type derivatives) [19,24,26,27,35], and (ii) post-synthetic modification of the of inorganic surface of γ-or λ-ZrP by means of topotactic ligand exchange reactions with phosphonic acids [5,19,24,26,27,47] or carboxylic acids [32,33,45], respectively.…”

“…As we mentioned earlier, a layer of phosphates sustains the zirconium metals whose apical bonds are bonded to negative and neutral basic species, both pointing to the interlayer space (bottom of Figure 1). In the starting lambda structure, each zirconium is typically bonded to chloride anion and neutral Phosphoric Acid Industry -Problems and Solutionsdimethylsulphoxide molecule [48,49] which, in principle, can be replaced by any organic chemical structure, that is, carboxylates and amines, in a topotactic manner [32][33][34]45]. Recently, we have prepared several new soft and rigid phosphate-based λ-type organic-inorganic two-dimensional (2D) and 3D frameworks with variable porosity [10,20,32,34].…”