SU1129212A1 - Cobalt (iii) monohydrate,nitrates,asymmetrical trans-bis-dimethylglyoxymatodi (chalcogenecarbamide) and process for preparing same - Google Patents

Abstract

1. Monohydrates, nitrates, asymmetrical trans-bis-dimethylglyc simatode (chalcogen carbamide | cobalt (W) of the general formula NHj - C, n-NgK, 1n e N0, H, 0 XN-d dH, n, (; o-n -o X ch., / HtK KHj (L where XS, Se 2. Method of producing monohydrates of asymmetric nitrates of trans-bis-dimethylglyoxymathodi chalcogencarbamide) cobalt (III), t. l and h ay and the alkaline solution of the mixture dimethylglyoxime and cobalt nitrate, heated to 80–85 ° C, are neutralized with nitric acid to pH 1–2 and reacted with the corresponding chalcogen carbamide, followed by cooling down a mixture on ice and the isolation of a target product. 3. The method according to claim 2, wherein dimethylglyoxime, cobalt nitrate and chalcogencarbamide are taken in a molar ratio of f2-1: 2.

Description

1I

The invention relates to a new class of coordinated compounds based on cobalt (III) dioximines, namely, monohydrates of nitrates asymmetric trans-bisdimethylglyoxydimodi (chalcogencarbamide) cobalt {) of the general formula, H-0

Oh i,

- CH,

NO H | 0 -Y tfH,

 X

Htw khj

where X 5 (1), Se (P), which can be used in various fields of coordination chemistry, and also in the textile industry as catalysts for the reduction of bottom dyes with sodium hydroxy sulfonate with C i-4j.

The structure of trans-dioximines cobalt (III) with thiocarbamide is known for - compounds with (HA), Tb (, H (OH) 2T; o An N0.6, where B is monodeprotonated residue of methylcarbethoxyglyoxime, thiocarbamide. At) - parachloroaniline; both compounds are trans-dioximines with an octahedral environment of cobalt.

The aim of the invention is to create a new class of coordination compounds based on cobalt dioximines (1i) with thiocarbamide and its derivatives, containing a new combination of bonds.

This goal is achieved by the synthesis of cobalt (111) cocTaBa Co (DH) 2Xae trans-dioximines, where XqE Ti (0- (Tfjio), or selenium (Seu) -carbamide, in the structure of which the asymmetric arrangement of atoms of the complex cation is first realized by the general formula) .

The compounds obtained are light brown crystalline substances. Habit

29212J

The crystals appear as thin four, and often hexagonal plates. Compounds are well soluble in polar solvents 5 (water, alcohol, insoluble in nonpolar. According to the measurement of magnetic susceptibility at 300 K, they are diamagnetic, which indicates the formation of trivalent cobalt complexes.

The method of obtaining compounds (l) iHp) consists in the interaction of a neutral alkalized NMO hot alkaline solution of a mixture of dimethyl15 glyoxime and cobalt nitrate with chalcogen carbamide, followed by cooling the reaction mixture on ice. With this, strict compliance with the technical regime is important:

20 temperature range 80-85 ° C; pH after neutralization in the range of 1-2; the ratio of the interacting substances (dimethylglyoxime, cobalt nitrate, .halcogencar25 bamide) 2-1: 2, the selection of the target

products by planting crystals from the reaction mixture on ice. I.

Example 1. Heated to 80 C solutions of 2.3 g (o, 02 mol) of dimethyl tilglyoxime in 20 ml of IN sodium hydroxide and 2.9 g (0.01 mol of cobalt nitrate hexahydrate in 5 ml of water and mixed and heated for another 5 minutes Then the solution is neutralized 1N

5 with nitric acid to pH 1 and a solution of 1.5, 02 mol of) thiocarbamide is poured into 10 ml of water heated to. The mixture is immediately cooled on ice. In this case, homogeneous light brown horizons (1) fall out, the substance is filtered off, washed with ethanol and dried in air. VyvodO) for all variants of the synthesis are presented in table. one.

 Paydeno,%: C 22.92} H 4.34; Co 11.21, - N 24.03; S 12,, 01 HjO 3.45.

C „H CoN, 08S2.

Calculated,%: C 23.04; H 4.64; 0 with pro; N 24.18; S 12.30, 3.46.

PRI mme R 2. Heated to 80 ° C solutions of 2.3 g (o, 02 mol) of dimethylglyoxime in 20 ml of IN sodium hydroxide and 2.9 g (0.01 mol) of hexahydrate 5 of cobalt nitrate in 5 ml of water are mixed and heat for another 5 minutes. Then the solution is neutralized IN with nitric acid to pH 2 and the solution is poured

2.5 g of selenocarbamide in 15 ml of water heated to 80 ° C. The mixture is immediately cooled on ice. In this case, uniform brown plates (it) fall out, the substance is filtered off, washed with ethanol and dried in air. Output (11) for all variants of the synthesis are presented in table 1.

Found,%: C 19.30; H 4., 02; From 9.29; N 20.33; Se 25.39; 3.00 CoN.OgSe

Calculated: C 19.52; H 3.93; Co 9.58; N 20.49; Se 25.67; 2.93

ilo according to the thermogravimetric analysis of compound (1) and (105 ° C (1) and (ll) are dehydrated, at 185Pc () and 147 ° C (P), the complexes are destroyed with disintegration inside, the complex cation is cracked.

In the electronic absorption spectra of aqueous solutions (1) and (P), two bands with fl 237, 340 nm and 240, 360 nm, respectively, are observed, which is characteristic of all cobalt trans dioximes (llt containing two chalcogen carbamide molecules.

According to the IR absorption spectra, the presence of compounds (l) and (RI) in the spectra (CS 730 and (C-Se) 690 CM, -5 (N-HV 3400-3200 CM, S (NH2) 1640-1650 cm indicates coordination chalcogen carbamides to the central cobalt atom by means of a sulfur atom (selenium).

The crystalline and molecular structure (1) and (c) is proved by X-ray structural analysis and is presented in the appendix. Crystallographic characteristics (L and (P) are presented in Table 2.

The structures are constructed from the complex cation of the HOi anion and water molecules. Complex

cations are asymmetric. Atom Co coordinates 4 octahedra of nitrogen atoms

two residues of dimethylglyoxide and 2 atoms of sulfur (selenium) of chalcogen / carbamide molecules. The intramolecular hydrogen bonds formed between the oxygen atoms of the oxime groups are: 0, -0, 2.50; О ,, -, 47,4 (1; О, -, 48, 0, j-, 51 (ll).

Q The water molecule and the WO anion are located between the complexes of the structure and participate in the formation of intercomplex. clear hydrogen bonds. The planes of two molecules: alkogenkarbamida

almost mutually perpendicular. The interatomic distances and valence angles of the complex cations (1) and (P) are listed in Table. 3

I

0 The positive effect of the invention is to create a new class of chemical compounds that differ from the known trais-dioximinocobalt (111) containing two molecules of chalcogen carbamide in the internal coordination sphere, because in the complex cation the atoms of the flat, chalcogen carbamide molecules are oriented asymmetrically relative to each other and the equatorial fragment. This leads to an improvement in the practical use of the properties of the isomers obtained, in particular, an increase in the solubility in water and alcohol, and a lower temperature stability. Exactly . 5 this circumstance allowed to achieve a positive effect, not. The aim of the invention is the following: substances that can: replace their analogs s and, as accelerators of recovery, vat dyes in compositions d ° 1 of dyeing fabrics, are obtained. ,

one,

Tables a. . one

2.3

2.3

11.7

5 1 4il7 / 80

80 80 85

1.5

5 2 4,22 / 81 7,6

10 1.5 20.30 / 78

The reaction time of cobalt nitrate with dimethylglyoxime.

Indicators

monoclinna

, 905 (nm)

480

, 141

, 34 (hail)

Spatial group

The number of formula units

.-

Density, m

Continued table. one

Ta blitz 2

Compounds

Singoni

R

triclyin

, 978 (nm)

 558

, 935,) (75.45 .37

PJ

2 1.97

.Table 3

1C

1129212 Continued table. 3

Claims (3)

1. Monohydrates, nitrates, asymmetric trans-bisdimethylglyc ^: simatodi (chalcogen carbamide) cobalt (ill) of the General formula ΝΟ, Η, 0 CH, where X = S, Se ’ 2. A method of producing monohydrates of nitrates of asymmetric trans-bisdimethylglyoximatodi (chalcogen carbamide) cobalt (III), characterized in that the alkaline solution of a mixture of dimethylglyoxime and cobalt nitrate, heated to 80-85 C, is neutralized with nitric acid to pH 1-2 and subjected to interaction with the corresponding chalcogen carbamide, followed by cooling the reaction mixture on ice and the allocation of the target product. 3. The method of pop. 2, characterized in that dimethylglyoxime, cobalt nitrate and chalcogen carbamide are taken in a molar ratio of * 2-1: 2. trans-bis-dimethylglyoximato nitrate (thiocarbamide) (parachloraniline) cobalt (III) - Report of the Academy of Sciences of the USSR, 1975, vol. 222, p. 83.