Azizova Asmat Nizami - The Institute of Catalysis and Inorganic Chemistry named after
acad. M.Nagiyev of the National Academy of sciences Azerbaijan,e-mail: iradam@rambler.ru
Changing properties of liqands
during coordinating with metals
Rzayeva Suraya Jabar – Azerbaijan Medical University research assistant, e-mail: iradam@rambler.ru
Changing properties of liqands
during coordinating with metals
Gasimov Shmid Guseyn, Azerbaijan Medical University, Senior Research Fellow, e-mail: iradam@rambler.ru
Changing properties of liqands
during coordinating with metals
Gasanov Khudayar Ismail, Azerbaijan Medical University, Doctor of chemistry, professor e-mail: iradam@rambler.ru
Changing properties of liqands
during coordinating with metals
CHANGING PROPERTIES OF LIQANDS DURING COORDINATING
WITH METALS
It
is known that sulfur- and nitrogen-containing ligands have high tendency to
form complexes with platinum (II) and palladium (II). Synthesis of mixedligands complex
compounds of platinum (II) with tetramethylethylenediamine – (CH3)2N
(CH2CH2) N (CH3)2 (tetmen) and ethylenditiodiacetic acid HCOOS
(CH2CH2) SCOOH (HSSH), as well as determining of dependence of the
properties of complexes on the nature of central atoms presents
great interest for biocoordination chemistry.
In
the subacid conditions the action of an equimolar amount tetmen, HSSH and [Pd
(NH3)4] Cl had been obtained a pale yellow crystalline
substance – [Pd (tetmen) (HSSH)] Cl2•3H2O. The
composition and structure of the synthesized complexes studied by
modern physico-chemical methods. The
resulting material is soluble and have a low-grade acidic properties. At the
potentiometric titration of suspension [Pd (tetmen) (HSSH)] Cl2•3H2O
against the background of 0.3M NaNO3
there is a jump in the
titration curve in the area of two equivalents of added alkali, which corresponds to simultaneous titration of the two carboxyl
groups. In the acidic medium at the
same time there is a protonation of both atoms of nitrogen.
Determination of acid dissociation constants of the complex [Pd (tetmen) (HSSH)]Cl2•3H2O was
carried out on the basis of titration data of solutions with concentration
of 1.0•10-3 mol/l on the background of 0.2 m
KCl,
taken
into account simultaneously titration of the two hydrogen ions. The infrared spectrum of the complex [Pd (tetmen) (HSSH)] Cl2 • 3H2Ohas been shot in the areas 200–500 and 1000–2000 cm-1.
In the IR spectrum of the complex absorption
bands with frequency 349, 356 and 422 and 430 cm-1 had been
attributed respectively to the chemical bonds of Pd-S and Pd-N. Two absorption bands for single links indicate their cis-location. Other observed three
absorption bands in 1716, 1728 and 1770
cm-1 have a varying
intensity, which are assigned to nÑÎÎÍ protonated carboxyl group.
It
should be noted that the complex – [Pd (tetmen) (HSSH)] Cl2 • 3H2O
in alkaline medium deprotonation of the carboxyl group does not occur, i.e.
there is no coordination carboxyl group to the central atom.
In
the IR spectrum of the crystalline hydrate absorption bands had been present, which
can be attributed to nÎÍ –3420 cm-1 and dÎÍ –1640 cm-1 of the crystallization water.
Thermal
analysis of the complex shows that at the temperatures above 1400°C three water molecules are segrerate.
On the thermogram of anhydrous substance on the DTA curve disappears
endothermic peak associated with the detachment of water from the crystalline.
It should be noted that if the anhydrous product to sustain in a desiccator
over water, within a day the substance
absorbs two molecules of water again.
The
obtained complex – [Pd (tetmen) (HSSH)]Cl2•3HO with cis-structure
has radioprotective and moderate psychoactive properties.
Studies
have shown that regardless of the nature of the central atom, it can get
complex with a given structure depending on the nature of the ligand.