SU806686A1 - Three-ligand nickel dioximines and their preparation method - Google Patents

Description

(54) -TREHELIANS 1SH (JSIMINA NICKEL (11) AND METHOD OF THEIR RECEPTION)

The invention relates to a new class of compounds — triligand nickel (II) dioximines, of the general formula T Xi. where X is 1/1504, Ce04. , ftr, which can be used as magnetic and semiconductor materials, polymerization catalysts, biologically active preparations, and cno them. Advantages of the compound dvl (gandal dioximines of divalent nickel (11) of the general formula C N i, where (A is dioxymate ion) 1G, having a square-planar structure and being a diamagnetic 1I. The method for their preparation is based on the interaction of nickel (acetate) salts with Comparing the structural formulas of the compounds (T) and the known compounds (II), the differences between these two classes of compounds are obvious: 1. Compounds (I) are the third group of compounds in the alcohol, water-alcohol or alcohol-pyridine solution. ligands, while all known nickel dissimins contain only two o-dioxime residues; 2. Compounds (I) are octahedral, compounds (II) are square-plane; 3. Compounds (1) are paramagnetic (.B) Compounds (II) are diamagnetic, which is a consequence of their different structure; 4. Compounds (1), in contrast to the known dioxime complexes of nickel, contain no mono-anisides — di (zsimov, but fully protonated molecules.

Thus, the nature of the chemical bond itself in this class of compounds is fundamentally different from that realized in known dioximes: the bond is carried out without replacing the proton metal with ot-dioximines.

The closest compounds are iron triligand dioximines of the general formula:

Гее (1,2-cyclohexanioxime) d} X, where X is anion 2.

The method of obtaining the known compounds is based on the interaction of the ferrous iron salt with 1,2-cyclohexanedione dioxime in the presence of methanol at a pH of 0.1-1.0. Copper iron is introduced into the reaction in the form of an aqueous solution, and 1,2-cyclohexanedione dioxime - in the form of alcohol.

The purpose of the invention is the synthesis of a new class of triligand compounds of divalent nickel.

This goal is achieved by the fact that, in order to obtain triligand dioximines of divalent nickel, the nickel salt (11) is reacted with 1,2cyclohexanedione dioxime in the presence of alcohol at a pH of 0.05-O, 7. I pH values are measured on a pH 340 pH meter-millivoltmeter with a scale reference

The prospect of using the proposed compounds is determined by a new chemical structure, which is reflected by the formula CL).

The proposed triligand compounds of divalent nickel (1) are fundamentally different from the iron dioximines given:

1. In the electronic configuration of complexing ions: (3 for ferrous iron and 61 for two-grade nickel; 2. In magnetic properties: all iron compounds are diamagnetic, while the proposed compounds (1) are paramagnetic (MB);

3. Behavior in solutions based on the fact that compounds (1) as compared with iron compounds are obtained at much more acidic pH values (from O, O5 to O, 7). In the case of triligand iron compounds, the latter are dissolved in water even at right pH / 5-6. In the neutral and weakly alkaline medium, the first separation of one proton occurs, which leads to the formation of compounds of the type iJFe (1,2-cyclohexanedione-dioxime-H) (1,2-cyclohexanedione-dioxime) 13 X, and then the second

the formation of the Fe none-electrolyte complex (1,2-cyclohexanedione dioxime-H) 2 (1,2-cyclohexanedione dioxime), but both the hexa-nitrogen environment of the iron atom and the octahedral configuration of the corresponding compounds are preserved. For triligand nickel dioximines (I), the deprotonation process is ve- det to decomposition of the existing octahe of the complex of the complex with the formation of a very stable planar bright red diamagnetic compound of the divalent nickel INA (1,2-cyclohexanedione dioxime-H) 23 and proceeds at a pH close to O.

The structure of the proposed compounds is shown by PC spectra, which show the absence of absorption bands of intramolecular hydrogen bonds characteristic of previously known dioxides.

Nickel simines, as well as the study of magnetic properties: the magnetic moments found are characteristic of octahedrally coordinated. .The particular structure of the proposed class of

The studies suggest the possibility of their use as models of magnetic dielectrics.

The nickel salt is introduced into the reaction in the form of an aqueous, ethanolic or methanol solution, and 1,2-cyclohexanedione dioxime as an alcoholic solution, and the prerequisite is to preliminarily bring the pH of the reactive solutions to O, 5-Oj7, unlike the preparation of the corresponding dioximines iron, where the order of addition of the acid does not affect the formation of the desired product. Good results are obtained by mixing the components in the solid phase, followed by wetting with pre-acidified ethanol.

The method for preparing the proposed compounds differs from that known for ferrous compounds:

1. To obtain nickel compounds, a much more acidic medium is necessary (from O, O5 to 0.7):

2, Has the value of the order of addition of the acid to the reacting solutions: in the case of iron compounds (11), the required pH value is achieved after a simple displacement of the components, while for nickel (II) compounds to avoid

the formation of a bright red bis (1,2-cyclohexanedione-nixato) nickel (II) requires a preliminary acidification of the solutions.

Claims (2)

Claim 1. Three-ligand nickel dioximines of (11) _ general formula. H> n, / C— II · & ΟΆ m - and Η0Ν where X-1/2 bO ^ Sv 0 ₄ , Vt. 2. The method of producing compounds according to π. 1, characterized in that the Nickel salt (11) is reacted with 1,2-cyclohexanedione dioxime in the presence of alcohol at a pH of 0.050.7.