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IK spectroscopic studying of complexes Ni2 +, Cu2 +, Zn2 + with L - D-КМАК and L-КМГК

In the present work have been investigated IK spectrums L-КМАК, D-КМАК and L - KMGK in the form of them protonirovannyh complexes with Ni (II), Cu (II) and Zn (II).

Samples for shooting IK of spectrums prepared in the form of tablets which pressed from a mix of investigated substance and KBr. Spectrums removed on IK Fourier-spectrometer FSM 1202 Open Companies "Инфраспек".spektry removed in a range 4000 - 450 sm-1, considered areas 3600 - 2500 sm-1 and 1800 - 800 sm-1 belonging to absorption bands of groups About — H, N — H, C = About, C-Oi C - N which are the basic source of the information on investigated complexes.

As Ik-spectra of L-isomers of the amino acids used for synthesis of optical isomerides kompleksonov, i.e. L - aspartic and L-glutaminovoj acids have been studied. For comparison, in view of absence in our disposal D-ISOMERS, spectrum D, L-glutaminovoj acids has been removed. Spectrums removed on IK spectrophotometer SpectrumOne (PerkinElmer). Samples for all measurements prepared in the form of tablets which pressed from a mix

Investigated substance and KBr. For example, took by turns a shot nearby 1∙10-4 mole In,-glutaminovoj, L-glutaminovoj, L-asparaginovoj acids and mixed about 0,72 g of bromide of potassium. In a porcelain mortar a mix carefully pounded and pressed in a mould, receiving a semi-transparent tablet [7].

Some of the removed spectrums are shown on fig. 5.4.1, other spectrums are yielded in the appendix. The characteristic frequencies of the major strips received as a result of decoding of all removed spectrums, are presented to tab. 5.4.1.

Fig. 5.4.1. Ik-spectra of complexes 2п+В,-KMAK (green), Zn+D-КМАК (brown), Zn+L-КМАК (dark blue).

Fig. 5.4.2. A complex Ik-spectrum ^ with L-КМГК.

Table 5.4.1.

The major characteristic frequencies IK of spectrums of complexes Ni (II),

Cu (II) and Zn (II) with KMAK, KMGK (sm-1).

Connection vO-Hs vob. vO-Hs An elm. vN-H vN-H + vC=O ^.as vC-O vC-O ^.as vC-N vC-N
L-КМАК
L-asp 3490 3000 3450 2500 1720 1510 1350 1150 805
H3X 3598 3000 3437 2477 1710 1638 1398 1082 890
H [NiX] ∙2H2O - 2940 3284 - - 1587 1404

1315

1118 836
H [CuX] ∙H2O - 2935 3180 - - 1605 1379

1296

1134 979
H [ZnX] ∙2H2O - 2938 3271 - - 1602 1407

1307

1088 908
D-КМАК
H3Y 3493 3003 3408 2658 1690 1643 1423 1153 899
H [NiY] ∙2H2O - 2938 3281 - - 1593 1412

1313

1096 906
H [CuY∙H2O] ∙H2O 3500 2933 3264 - - 1615 1408

1303

1098 905
H [ZnY∙H2O] ∙H2O 3506 2930 3268 - - 1613 1409

1314

1125

1075

937
Glu
H3L-Glu - 3050 3400 2650 - 1650 1350 1100 810
H3L, D-Glu 3574 3055 3469 2650 1711 1667 1356 1105 810
L-КМГК
H3Z - 3058 3432 2663 - 1660 1423 1130 808
H [NiZ] ∙2H2O - 2930 3413 2425 - 1600 1370 1080 640
H [CuZ] ∙1H2O - 2933 3432 - - 1628 1388 1129 785
H [ZnZ] ∙2H2O 3500 2925 3333 - - 1590 1408 1103 745

At interpretation IK of spectrums studied kompleksonatov metals of optical isomerides the empirical method of reference of characteristic frequencies, by comparison IK of spectrums of studied objects, kompleksonov and initial amino acids was used. In the literature results IK of spectroscopic studying racemic KMAK and it kompleksonatov metals which are structural analogues L-КМАП, D-КМАК are published, and also their complexes [104].eti data have helped to manufacture reference of strips simply enough.

For reference of absorption bands
Complexes L-КМГК used results of interpretation of spectrums L-КМАК which is its homologue.

In Nikolsky V. M and Knjazevoj N.E.'s works as method IK of spectroscopy it is proved, that KMAK has betainovuju structure not only in a solution, but also in a solid kind [104].

In all removed spectrums strips of valence vibrations of the secondary amino groups in the field of 3450-3200 sm-1 and weak strips connected-OH grupp3000-2500 sm-1, characteristic carboxylic acids for spectrums [84] are found out.

On absence of absorption bands-NH} in the field of 3000-2250 sm-1 (characteristic for amines) [84, 121,122] in complexes of investigated ligands with metals it is possible to draw a conclusion that the-carboxyl group proton is not localised on an amino group. Hence, in all these complexes there is no betainovaja a structure, metal substitutes atoms of hydrogen of carboxyl groups-COOH, and also communicates a co-ordinate linkage with atom of nitrogen (formation of soluble chelate salts) [130]. As the additional proof of it the fact can serve, that free isomers kompleksonov have absorption bands in the field of 1714-1724 sm-1 which belong to the not ionised group-CH2 - COOH.

In complexes Сu2+иZп2+cD-КМАКнаблюдается absorption band free - IT groups [82, 123], hence, this group is not co-ordinated by ions of the studied metals so, rassmatrivaemyjizomer in these complexes is tridentatnym a ligand - the atom of nitrogen and two a-carboxylaled groups participates in coordination aminnyj.

In complexes Zп2+cL-КМАК and L-КМГК, Cu^cL-КМАК and L-КМГК and so zheNi2+cL - D-КМАК and L-КМГК, there is no strip free - IT groups, hence this group is co-ordinated by ions of considered metals so, considered isomers in these complexes are tetradentatnymi ligands - in coordination participate aminnyj atom of nitrogen and all three carboxylaled groups. Taking into account results of thermogravimetry, on fig. 5.4.3 constitutional formulas of complexes D-КМАК with ions of copper, zinc are presented

And nickel, on fig. 5.4.4 constitutional formulas of complexes L-КМАК with ions of copper, zinc and nickel, on 5.4.5 constitutional formulas of complexes L-КМГК with

Ions of copper, zinc and nickel.

Fig. 5.4.3. Constitutional formulas of complexes Cu+D-КМАК (), Zn+D-КМАК

(), Ni+D-КМАК (.

Fig. 5.4.4. Constitutional formulas of complexes Cu+L-КМАК (), Zn+L-КМАК

(), Ni+L-КМАК (.

Fig. 5.4.5. Constitutional formulas комплексовCu+L-КМГК (), Zn+L-КМГК

(), Ni+L-КМГК (.

Being based on results of calculation of constants of stability of complexes, thermogravimetry and Ik-spectroscopy, it is possible to assume, that differences in coordination of optical isomerides with ions of metals are defined by steric difficulties. So, for example, in case of coordination of metals with L - derivatives all 4 reactive groupings have possibility to form communication with metal since are over a plane in which settles down hiralnyj the centre.

At D - derivatives in that hemisphere where there is a metal settle down 2 α - carboxyl groups and an amino group, and v-karboksilnaja the group stays in an opposite hemisphere that does not give the chance to this group to be co-ordinated with a metal ion.

On fig. 5.4.6 it is schematical izobrazhenoraspolozhenie reactive groupings L - and D - isomers concerning a plane of symmetry without the plotting of communications with metal.

Fig. 5.4.6. Structural formulJu-KmAk () and L-КМАК ().

As, observable spectrums of complexes of the same metals with optical isomerides differ on absorption intensity [3].

On known literary data [33] to find out direct proofs of bonding Me-Ni Me — About it is not obviously possible since they yield weak absorption bands in the field of 350-450 sm-1 where it is difficult to distinguish them from each other (this site of a spectrum it is impossible to investigate by means of the Ik-spectrometer available in our disposal). However, in modern sources [124-126] it is underlined, that communication Me — About can be found out in the field of 600-400 sm-1. As well Peshkova T.V. with soavt., believe, that absorption band in the field of 700-600 sm-1 belongs v (NH2) torsional vibration of functional group NH2 connected with an ion of zinc, and additional strips in the field of 800-600 sm-1 of fluctuations carried kt (HpO), estimate communication of metal with oxygen [127]. In all spectrums removed by us is
Absorption bands in similar characteristic areas on the basis of what it is possible to make also the assumption of coordination of atom of zinc with carboxyl groups and atom of nitrogen.

Strong sour properties kompleksonov, derivative dicarboxylic amino acids, are caused by presence of a-carboxyl groups of dicarboxylic acids. It speaks negative inductive effect uksusnokislotnyh the rests containing at a-carbon atom the substituent of type - (CH2) nCOOH, where n = 1 for aspartic and n = 2 for glutamic acids [7].

At comparison IK of spectrums powdery L-glutamic acid and D, L - glutamic acid and as L-asparaginovoj acids firms "Reanal" (Hungary) it has been positioned, that in solidity they have betainovuju structure. It proves to be true the absorption bands which are present at spectrums of both isomers in the field of 2700 - 2250 sm-1. More expressed absorption band at 1376 sm-1 at L-isomer emphasises zwitter-ion presence (—NHz — CHRCOO-), capable to form hydrogen bridges. Proceeding izetogo the conclusion can be drawn, that in a L-isomeasure the closed circuit of the ionised a-carboxyl group and protonirovannoj amino groups at the expense of formation of intramolecular hydrogen bridges with a water molecule [128, 129] as we have found out and at L-КМАК [96] is formed.


Fig. 5.4.7. IK spectrums of L-glutamic acid (2) and E,-glutaminovoj acids (1) in a range of frequencies of 3500-2000 sm-1.

Fig. 5.4.7. IK spectrums of L-glutamic acid (2) and E,-glutaminovoj acids (1) in a range of frequencies of 1800-400 sm-1.

Fig. 5.4.8. IK a spectrum of L-aspartic acid.

6.

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A source: Biberina Evgenie Sergeevna. COMPLEX FORMATION OF SOME ZE-METALS WITH L-, D-FORMES H- (CARBOXYMETHYL) ASPARAGINOUS AND L-N- (CARBOXYMETHYL) ACID GLUTAMINE. Thesis for the degree of candidate of chemical sciences. Tver - 2018. 2018

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