The way to obtain tetrakis-3(methoxo)-(methoxo)- pentakis(acetylacetonato) copper (ii) ree (iii) barium


(57) Abstract:

Usage: in ORGANOMETALLIC chemistry. The inventive product: for example tetrakis-M3(methoxo)-(methoxo)pentakis(acetylacetonato)copper (II), dysprosium (III), barium, CF Cu3VA2Dy34H63ABOUT19, EF. MB(298K) - 9,84; TRazlog.240oC. Reagent 1: copper nitrate Cu(NO3) 3BUT. Reagent 2: nitrate R33. Reagent 3: acetylacetone. reaction conditions: the interaction of reagents 1 and 2 in absolute methanol in the presence of formic ether by heating in a water bath followed by the addition of reagent 3 at pH 8, generated by the addition of pyridine. 3 tab., 3 Il. I

The invention relates to a method for heterometallic acetylacetonates, containing atoms of copper, barium and one of rare earth elements (REE) in the ratio of SR:BA:RA 3:2:1. These substances are after low-temperature pyrolysis and subsequent heat treatment to form a polycrystalline ceramic structure of perovskite having superconducting properties at temperatures above TKipliquid nitrogen.

A method of obtaining multi-core heterometallic acetylacetonates containing atoms honey is(60oC) methanolic solution of anhydrous copper chloride(P), oxide of rare earth element, barium hydroxide and acetylacetone, taken in the ratio 3:1:2:6. The process of education goes scheme

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Complexes B2[Cu3La(OCH3)8La(OCH3)8(C5H7O2)5] and Ba2[Cu3Eu(OCH3)8< / BR>
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The proposed mechanism of formation of heterometallic complexes can be represented by the diagram

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The mechanism associated with the initial formation in the reaction mixture in the presence of proton-acceptor reagent piperidine coordinationcogentin methoxo-acetylacetonates of copper (II) and rare earth element (stages a and b), which react with each other with the formation of the tetrakis-(methoxo)-metacapitalism (acetylacetonato)trimmed (II), REE (III) anion, a negative charge which is neutralized by ions of barium. Introduced into the reaction mixture together with the original nitrates of copper and REE crystallization water molecules go to the hydrolysis ortogonalnogo ether:

HC(OC2H5)3+ 2H2O __ HCOOH + 3C2H5OH, and resulting from the reaction of formic acid is neutralized the security of their synthesis within 40-45 minutes, it is simple in execution, the starting materials are available, and the resulting reaction by-products remain in the mother solution. In addition, this method extends the range RE entered the complex.

Obtained by the claimed method compounds are lilac in color. They are insoluble in alcohols, benzene, chloroform, ether, acetonitrile, acetone, sparingly soluble in dimethylformamide, dimethylsulfoxide, water destroyed.

Example 1. Getting tetrakis-3-methoxo(methoxo)pentakis(acetylacetonato)copper (II), yttrium (III) barium.

To a solution containing 3,63 g (15 mmol) of Cu(NO3)23H2O and 1.92 g (5 mmol) of Y(NO3)36H2O in 60 ml of absolute methanol is added 1,71 g (10 mmol) of Ba(OH)2and 30 ml ortogonalnogo ether. The resulting reaction mixture is heated on a water bath (~60o(C) under reflux for 30 minutes. Then she added 2.55 ml (25 mmol) of acetylacetone and piperidine to pH~8, after which the contents of the flask continue to heat (~60o(C) with constant stirring; the solution appears homogeneous crystalline product lilac color, which is filtered off on a glass filter, washed with absolute methanol, EPA nitrates of rare-earth elements, get II-IX.

In table. 1 physico-chemical properties of selected compounds, and table. 2 information about downloading the source, the output end of the substances and the time of their synthesis.

Visual microscopic examination of the synthesized complexes indicates their phase homogeneity. They crystallize in the form of thin prisms (needles), the size of which does not exceed the 0.01 x 0.01 x 0,03 mm

To establish the identity of the substances, their composition and research of the peculiarities of the I-IX were used methods of x-ray diffraction analysis, IR, EPR spectroscopy, minatojima and thermogravimetry.

X-ray analysis of complexes obtained by the claimed method and similar substances synthesized in a known manner, identical (Fig. 1). The changing nature of the cation of the rare earth element Ln3+causes only small differences in intensities of reflections. This suggests that the studied heteronuclear acetylacetonates regardless of how they obtain form an isostructural series with Ln=Y,La,Nd,Sm,Gd,Tb,Dy,Ho,Yb.,

It should be noted that the diffraction pattern is allocated a number of reflections with great intensity and reflections with intensities neznachitel sabyasachi asub11,476 csub9,369 , and the values of these parameters are practically independent of the nature of rare earth element.

Isostructural multicore heterometallic acetylacetonates by the well-known and inventive ways, finds additional confirmation and the similarity of their IR spectra. The presence of absorption bands in the regions 1580-1570 cm-1, 1560-1430 cm-1and 460-300 cm-1characterizing respectively the stretching vibrations(C-C),(C-O)(M=Cu,Ln)), testify according to literature data (Nakamoto K. Infrared spectra of inorganic and coordination compounds. K. Mir, 1966 S. 411), that in the investigated heteronuclear complexes of acetylacetone acts as bidentates chelating ligand and forms with metal ions the six-membered metallocycle. It should be noted that in Inspectah all complexes is intense absorption band at 1150-1020 cm-1related to(C-O)methoxo groups. This position of the strip according to the literary data /56.2/ indicates that methoxo group in the study heteronuclear the acetylacetonates is a bridge and combines the metal atoms with the formation of multi-core connection. In addition, a number of areas, what that suggests for them a similar tetrahedral tetramer structure.

Magnetochemical investigation of complexes of l-IX at room temperature showed that all of them are paramagnetic (PL. 1). The obtained experimental values of the effective magnetic moments ((eff)) per molecule of (SR, BA,Y) and (Cu, Ba, La.)-containing acetylacetonates at room temperature is of 3.10 and 3.21 M b, respectively.

Study of the temperature dependence of the magnetic susceptibility for (Cu3Ba2La) -containing complex showed that at low temperature magnetic susceptibility increases monotonically from'Mrc1065196,8 cm3/mol (at T 298 K) to'Mrc1068556,8 cm3/mol (T 106 K), witheffdecreases from 3,21 M B. to 2.60 M. B. indicating the presence of an exchange interaction between ions of copper (II) complex. These EPR spectroscopy confirm the conclusions made on the basis of magnetic measurements: for all complexes the spectra are similar and consist of a single singlet with geff, 2,1 in the field 2970-3120 e whose width is almost independent of temperature.

Thus, Soedineniya are isostructural and have a tetrahedral structure.

Thermogravimetric analysis I-IX revealed for all complexes are almost identical course of thermal transformations: when 220-230oC exothermic effect begins, and at 380-400oWith the ends of thermal-oxidative degradation of the organic part of the molecule of the complex. The temperature of the maximum speed of this process lies in the interval 230-265oC (PL. 1) and decreases when moving from I to IX.

The phase composition of the products of low-temperature (~400oC) pyrolysis of I-IX according to REntgen-diffraction analysis identified the same type of substances CIO, Ln2O3and VASO3(Fig. 2). Elemental chemical analysis of these compounds suggests maintaining the stoichiometry of si:VA:Ln 3:2:1.

To obtain phase 3:2:1 orthorhombic modification products of low-temperature pyrolysis II and VII were annealed in a stream of oxygen at a temperature of 920oC for 2 hours and then cooled to room temperature. X-ray phase analysis of the final products have established the presence of the orthorhombic modification LnBa2Cu3O7-(Fig. 3).

The superconducting transition temperature of the fine powder DyBa2Cu3O7-was determined using Takim way the proposed method for heterometallic acetylacetonates, containing atoms of copper, barium and one of rare earth elements in 6-7,5 times reduces the time of their synthesis and eliminates the possibility of contamination, in addition, while increasing their output (1.05-1.15 times) and expanding the number entered in the complex REE (with 5 to 9).

For one not described in the literature complexes (Cu3Ba2DyC34H63O19) developed a method of obtaining polycrystalline ceramics of perovskite structure, which is converted to the superconducting state at 94 K. TTT TTT

1. The way to obtain tetrakis-3(methoxo)-(methoxo)-pentakis(acetylacetonato) copper (II) REE (III) barium, where RSEU, La, Nd, Sm, Gd, Tb, Dy, Ho, Yb, characterized in that the nitrate of copper is subjected to interaction with the nitrate of the corresponding rare earth element in an environment of absolute methanol in the presence of ortogonalnogo ether, boiling and then adding to the reaction mass of acetylacetone at pH ~8.

2. The method according to p. 1, characterized in that the pH ~8 reach by adding to the reaction mass of piperidine.


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