HUO2PO4•4H2O (HUP) forms a laminar intercalate with butylamine, c = 29.30(5) Å, which accepts cationic metals in exchange for the n-butylammonium ions. Hydrated uranyl metal phosphates M(UO2PO4)2•nH2O (M = Mn, Co, Ni, Cu, Zn, Cd) are obtained by ionic exchange and were studied by thermal analysis and X-ray diffraction. The tetragonal structures of all these product compounds are derived from HUP. The diffuse electronic reflectance spectra of every sample show characteristic [Formula: see text] absorption bands. In the spectra of the Co, Ni, and Cu phosphates there are other bands in the 500–800 nm zone compatible with their observed aquocation transitions.
The ion exchange reactions of n-butylamine intercalates of tin(IV) hydrogen phosphate and hydrogen uranyl phosphate towards carbonatotetraamminecobalt(III), chloropentaamminecobalt(III), and hexaamminecobalt(III) have been investigated. Independent of the complex cation charges, the amounts of Co(III) complex exchanged by the n-butylamine intercalate of tin(IV) hydrogen phosphate are practically the same. With the n-butylamine intercalate of hydrogen uranyl phosphate, the ionic exchange was completed and the composition was fixed by the exchanged Co(III) complex. The layer charge densities of these phosphates justify the different ionic exchange behaviour observed towards the large complex cations. All the products were characterized by chemical analysis, X-ray diffractometry, infrared spectroscopy, diffuse reflectance spectroscopy, and thermal analysis.
RAFAELA POZAS-TORMO, SEBASTIAN BRUQUE GAMEZ, MAR~A MARTINEZ-LARA, and LAUREANO MORENO-REAL. Can. J. Chem. 66, 2849 (1988).The solids derived from HUP by substituting metallic ions for protons, take up Lewis base molecules (like NH3 and C4H9NH2) in the interlamellar space. The diffractograms of these inclusion compounds indicate that the host crystallinity was preserved.The infrared spectroscopy of the Ni, Co, Cu, Zn, and Cd intercalates revealed that part of the sorbate was protonated in the interlaminar space while the other part displaced the water in their coordination spheres. However, in the Mn derivative, no coordinated or free Lewis base could be detected: it was all in the protonated form.RAFAELA POZAS-TORMO, SEBASTIAN BRUQUE GAMEZ, M A R~A MARTINEZ-LARA et LAUREANO MORENO-REAL. Can. J. Chem. 66, 2849 (1988).On peut instrer des moltcules de bases de Lewis (comme le NH3 et le C4H9NH2) dans l'espace interlamellaire des solides que l'on obtient lorsqu'on remplace les protons des HUP par des ions mktalliques. Les diffractogrammes de ces composCs d'inclusion indiquent que la cristallinitt de l'h6te est prtservte.Les spectres infrarouges des produits intercalts comportant du Ni, du Co, du Cu, du Zn ou du Cd rtvklent que, dans l'espace interlamellaire, une portion du sorbate est protonte alors que l'autre portion a dCplacC I'eau de ses sphkres de coordination. Toutefois, dans les dCrivts du Mn, on n'a pas pu detecter de base de Lewis soit libre ou coordonnte; elles ttaient toutes sous la forme protonte.[Traduit par la revue]
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