Beata Bocian

Investigation of 5-chloro-2-methoxybenzoates of La(III), Gd(III) and Lu(III) Complexes

Abstract5-Chloro-2-methoxybenzoates of La(III), Gd(III) and Lu(III) were synthesized as penta-, mono- and tetrahydrates with a metal to ligand ratio of 1:3 and with white colour typical of La(III), Gd(III) and Lu(III) ions. The complexes were characterized by elemental analysis, IR and FIR spectra, thermogravimetric and diffractometric studies. The carboxylate group appears to be a symmetrical, bidentate, chelating ligand. The complexes are polycrystalline compounds. Their thermal stabilities were studied in air and inert atmospheres. When heated they dehydrate to form anhydrous salts which next in air are decomposed through oxychlorides to the oxides of the respective metals while in inert atmosphere to the mixture of oxides, oxychlorides of lanthanides and carbon. The most thermally stable in air, nitrogen and argon atmospheres is 5-chloro-2-methoxybenzoate of Gd(III).

Thermal and Spectral Behaviour of 5-chloro-2-methoxybenzoates of Heavy Lanthanides and Yttrium

Abstract5-Chloro-2-methoxybenzoates of heavy lanthanides and yttrium were obtained as di- or tetrahydrates with a metal to ligand ratio of 1:3 and general formula: Ln(C8H6ClO3)3⋅nH2O, where n=2 for Ln=Tb, Dy, Y and n=4 for Ln=Ho, Er, Tm, Yb, Lu. The complexes were characterized by elemental analysis, IR and FIR spectra, thermogravimetric studies, X-ray diffraction and magnetic measurements. The carboxylate group appears to be a symmetrical, bidentate, chelating ligand. All complexes are polycrystalline compounds. Their thermal stabilities were determined in air and in nitrogen atmospheres. When heated they dehydrate to form anhydrous salts which next in air are decomposed to the oxides of the respective metals while in nitrogen to the mixtures of carbon and oxides or carbon and oxychlorides of respective metals. The complexes are more stable in air than in nitrogen.The solubilities of yttrium and heavy lanthanide 5-chloro-2-methoxybenzoates in water at 293 K are of the order of 10–3 mol dm–3 The magnetic moments of the complexes were determined over the range 77–298 K. They obey the Curie–Weiss law. The values of µeff calculated for all compounds are close to those obtained for Ln3+ by Hund and Van Vleck. The results indicate that there is no influence of the ligand field of 4f electrons on lanthanide ions and the metal ligand bonding is mainly electrostatic in nature.

Thermal and Spectral Characterization of 5-Cholro-2-methoxybenzoates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)

The thermal stabilities of 5-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) were studied in air and nitrogen atmospheres. The complexes were obtained as mono-, di-, tetra-and pentahydrates with a metal to ligand ratio of 1:2 and with colours typical for M2+ ions (Mn-slightly pink, Co-pink, Ni-green, Cu-blue and Zn-white) and as polycrystalline compounds. When heated they dehydrate to form anhydrous salts which nextare decomposed to the oxides of the respective metals in air while in nitrogen to the mixtures of metal oxides and oxychlorides and carbon. The most thermally stable in air, nitrogen and argon atmospheres is 5-chloro-2-methoxybenzoate of Cu(II) while the least thermally stable is that of Co(II).

Thermal Stability of 2,3,4-, 2,4,5- and 3,4,5-tri- Methoxybenzoates of Light Lanthanides

The physico-chemical properties and thermal stability in air of light lanthanide 2,3,4-, 2,4,5- and 3,4,5-trimethoxybenzoates were compared and the influence of the position of –OCH3 substituent on their thermal stability was investigated. The complexes of these series are crystalline, hydrated or anhydrous salts with colours typical of Ln3+ ions. The carboxylate group is a bidentate, chelating ligand. The thermal stability of 2,3,4-, 2,4,5- and 3,4,5-trimethoxybenzoates of rare earth elements was studied in the temperature range 273–1173 K. The positions of methoxy groups in benzene ring influence the thermal properties of the complexes and their decomposition mechanism. The different thermal properties of the complexes are connected with various influence of inductive and mesomeric effects of –OCH3 substituent on the electron density in benzene ring.

Thermal Stability of 4-Chloro-3-Nitro- and 5-Chloro-2-Nitrobenzoates of Rare Earth Elements

The physico-chemical properties and thermal stabilities in air of rare earth element 4-chloro-3-nitrobenzoates and 5-chloro-2-nitrobenzoates were compared and the influence of the positions of the Cl and NO2 substituents on their thermal stabilities was investigated. The complexes of both series are crystalline, hydrated or anhydrous salts with colours typical of Ln3+. The carboxylate group in these complexes is a bidentate, chelating ligand. The NO2 group in the chloronitro complexes does not undergo isomerization. The thermal stabilities of the 4-chloro-3-nitrobenzoates of Y and the lanthanides were studied in the temperature range 273-1173 K, but those of the 5-chloro-2-nitrobenzoates of these elements were studied only at 273-523 K, because they decompose explosively above 523 K. The positions of the Cl and NO2 substituents on the benzene ring influence the thermal properties of the complexes and their decomposition mechanisms. The different thermal stabilities of the complexes are connected with various inductive and mesomeric effects of the Cl and NO2 substituents on the electron density in the benzene ring.

Thermal Properties of Light Lanthanide 2,3,4-trimethoxybenzoates

The light lanthanide 2,3,4-trimethoxybenzoates were obtained by the addition of an equivalent quantity of 0.1 M ammonium 2,3,4-trimethoxybenzoate to a hot solution of the light lanthanide nitrate, followed by crystallization at 293 K. The contents of carbon and hydrogen were determined by elemental analysis, with V2O5 as oxidizing agent, and the lanthanide element contents were established by the oxalic acid method. The complexes are anhydrous compounds with a metal to ligand ratio of 1:3 and the general formula Ln(C10H11O5)3. They have the colour characteristic of Ln3+. Their IR spectra were run in the range 4000–400 cm−1 on an M-80 spectrophotometer by using KBr discs. In these complexes, the carboxylate group appears to be a bidentate chelating ligand. The X-ray powder patterns were taken on a DRON-2 diffractometer, using Ni-filtered CuKα radiation, within the range 2Θ=5–80°, by the Debye-Scherrer-Hull method. The diffractograms indicated that the complexes are crystalline compounds. Their thermal stabilities in air were studied (273–1173 K) through the use of TG, DTG and DTA techniques, with an OD-102 derivatograph.The 2,3,4-trimethoxybenzoates of La and Nd decompose in two steps, but those of Ce, Pr, Sm and Eu in only one stop. The anhydrous 2,3,4-trimethoxybenzoates of La and Nd decompose to oxides with the intermediate formation of oxycarbonates, while those of Ce, Pr, Sm and Eu decompose directly to the oxides. The solubilities of these complexes in water (293 K) are in the order of 10−3moldm−3.

Spectrochemical and thermal behaviour of the 5-chloro-2-nitrobenzoates of rare earth elements

The conditions of the formation of yttrium and lanthanide 5-chloro-2-nitrobenzoates were studied and their quantitative composition and solubilities in water at 298 K were determined. They are anhydrous or hydrated complexes and their solubilities are of the order of 10-3 mol dm-3. The IR and X-ray spectra for the complexes were recorded. All complexes are crystalline compounds. Their thermal decomposition was studied. It was found that on heating above 523 K the complexes decompose explosively. Therefore their thermal decomposition was carried out in the temperature range 273-523 K. Hydrated complexes lose crystallization water molecules in one step. From the results it appeared that during dehydration process no transformation of nitro group to nitrito took place. Some of physico-chemical properties of rare earth element 5-chloro-2-nitrobenzoates were compared with 2-nitro- and 3-chlorobenzoates of those elements.