G. A. Kutyrev

Metal-polymer complexes of cobalt(II) and Copper(II) with hyperbranched polyester polycarboxylic acids

Hyperbranched polyester polycarboxylic acids of the second and third generations for use as high-efficiency complexing agents are synthesized. On the basis of these compounds, new metal-polymer complexes of cobalt(II) and copper(II) are prepared for the first time. As evidenced by IR and ERR studies, the central atom in these metal polycarboxylates occurs in the axially symmetric system MO6. The thermal stability of polymer copper complexes is improved with increases in the content of metal ions, the degree of functionalization, and the generation number of the polyacid platform.

Polynuclear Cu(II) complexes with hyperbranched polyester carboxylates

Polydentate carboxylate platforms based on polyester polyol Boltorn H, containing from 8 to 14 carboxy groups in terminal positions were obtained. A method of synthesis of Cu(II) polynuclear complexes with polyester carboxylates Boltorn H with a degree of substitution of 65 and 90% was developed.

Aminosilyl Derivatives of Hyperbranched Polyethers and Their Metal Complexes

Surface modification of nano-sized hyperbranched polymers with the fragments capable of effective complexation makes it possible to synthesize coordination compounds with practically useful properties. It was demonstrated previously that the modification is possible of non-toxic hyperbranched polyether polyols with acid fragments followed by the synthesis of the appropriate metal complexes possessing biochemical activity [1, 2]. Modification of hyperbranched polyether polyols with aminosilyl groups will provide multifunctional compounds that combine the ability to effective complex formation with the hydrogen bonding with biosubstrates. A similar approach was found very useful in creating next-generation drugs [3] and developing advanced optoelectronic systems [4]. The hyperbranched polyether polyols of the second generation were used by us as precursors of non-toxic, water-soluble polyether polyalkoxysilylamines. Modification of the terminal hydroxy groups of aminosilane was performed as follows: DOI: 10.1134/S1070363211050227

Polynuclear copper(II) complexes with polydentate nanoligands on the basis of aminoderivatives of the hyperbranched polyesters

Coordinationally active polydentate nanoplatforms on the basis of amino-modified hyperbranched polyesters containing 7 terminal amino fragments are synthesized. Synthetic procedure is developed and polynuclear Cu(II) complexes with polyesteropolyamines are prepared. Their composition and stability of the complex forms in DMSO-water solutions are evaluated. It is found that all the compounds obtained exhibit biological activity with respect to the induced asparagine proteinase of Candida albicans.

Structure of hyper-branched polyester polyol BOLTORN H2O-COOH. NMR data

The methods of one- and two-dimensional 1H and 13C NMR spectroscopy have been used to study the structure of hyper-branched polyester polyol BOLTORN H2O-COOH and complex Co12[BH20(COOH)] on its basis. It was shown that both compounds have non-stereoregular structure. Paramagnetic ions Co(II) are coordinated both on the surface of the molecule and near the core.

INTERACTION OF SULFENYL CHLORIDES WITH UNSATURATED ORGANOPHOSPHORUS COMPOUNDS: AdE3 REACTION MECHANISM AND REGIOCHEMISTRY OF ADDITION

Abstract As evidenced by 1H, 31P, and 13C NMR spectroscopy, phenylsulfenyl chloride, like phosphonosulfenyl chloride,1 adds to vinylphosphonates to produce a mixture of two regioisomers. Thermodynamic stability of β-chloroadducts is greater than that of α-chloroisomers. The 1,2-addition of C6H5SCl to isopropenyl-and styrylphosphonates and unsaturated thionophosphoryl compounds is regiospecific. Kinetic studies have established that the reactions might proceed by the AdE3-mechanism involving two molecules of an unsaturated reagent. The substituents at phosphorus and the carbon-carbon double bond in phosphonates affect the structure of the transition state in the limiting stage of the reaction, as does the medium. The effect of the organophosphorus group in the unsaturated reagent and sulfenyl chloride on the mechanism of the AdE-process has been analyzed.

Phosphorus-containing hyperbranched structures. Phosphorylation of hyperbranched polyols with 2-(diethylamino)-1,2,3-dioxaphosphinane

Kazan State University, ul. Kremlevskaya 8, Kazan,Tatarstan, 428008 Russia e-mail: Ilyas Nizamov@ksu.ru; nizamov@iopc.knc.ru b Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Centrer, Russian Academy of Sciences, Kazan,Tatarstan, Russia c Тatar State Humanitarian and Pedagogical University, Kazan, Tatarstan, Russia d Kazan State Technological University, Kazan, Tatarstan, Russia

Data of one- and two-dimensional NMR spectroscopy in the study of structure and nature of associations of hyperbranched polyester polyol Boltorn H20-OH

Structure of the hyperbranched polyester of the polyol BOLTORN H20-OH was studied by one- and two-dimensional 1H and 13C NMR spectroscopy in combination with the IR spectroscopy and semiempirical quantum-chemical calculations (method AM1). The polyol structure was shown not to be stereoregular. Three basic types of H-bonding interactions of intra- or intermolecular nature were revealed: C=O...HO, OH...OH, and C=O...HO...HO.

Synthesis of hyperbranched polyesterpolytrimethylsiloxanes

The number of reports on the synthesis of siliconcontaining dendrimers with a variety of organic components is steadily increasing. Carboxysilane, siloxane, silane, and so-called “hybrid” dendrimers have been obtained [1], and dendrimers have been also synthesized with inorganic polycyclosiloxane inner sphere and the organic layer on the periphery [2]. At the same time, the silyl derivatives of hyperbranched polyesterpolyols were not described.

Polydentate Nanoplatform Based on Hyperbranched Polyol Boltorn

In chemistry and technology now is rapidly developing a direction connected with the synthesis of nano-size hyperbranched polymers (HBP) and related functional derivatives possessing a wide range of practically useful properties [1, 2]. Nontoxic hyperbranched polyols of “Boltorn Н” series are promising objects for obtaining the metallocomplex compounds of biomedical application, with the polydentate polyol platform as a ligand [3, 4]. However, the complexes of “Boltorn Н” with the d-metal ions are very unstable. This may be a consequence of intraand intermolecular hydrogen bonding of hydroxy groups of the molecule that decreases significantly their steric accessibility and capability of complex formation [5, 6]. A route for overcoming this problem is the modification of HBP by means of substitution of OH groups by the groups more active toward metal ions.