Pub Date : 2022-03-25DOI: 10.33609/2708-129x.88.02.2022.85-115
S. Orysyk, V. Pekhnyo, V. Orysyk, Yu. L. Zborovskii, P. Borovyk, V. Mykhailo
The influence of competitive coordination, a tautomeric form of functionally substituted thioamides, conditions of synthesis and nature of the metal on the course of the reaction and structure of mono-, bi, and polynuclear complexes of 3d, 4d-metals is considered based on results obtained in the Department of "Chemistry of Complex Compounds" of the V.I. Vernadsky Institute of General and Inorganic Chemistry NAS of Ukraine, together with the staff of the Department of “Chemistry of Heterocyclic Compounds” of the Institute of Organic Chemistry NAS of Ukraine. The influence of ligand denticity, as well as conditions of complex formation on the structure of obtained complexes and their polymorphic modifications, was studied based on the reaction of d-metals with functionally substituted N, S- and O, N, S-containing thioamides. In addition, it is proved the influence of tautomeric forms of thioamides on the stereochemistry of coordination polyhedra: it is found that the thionic tautomeric form promotes the transposition of thioureas, while the thiol form promotes its cis-position in the square-planar of a polyhedron of 3d, 4d-metals in the structure of complexes. However, it was found that the thion tautomeric form leads to the formation of octahedral, while the thiol form to the square-planar of coordination nodes in complexes of Cu(II) and Ni(II), which are characterized by a change in coordination polyhedra (from square-planar and tetrahedron to octahedron) that depending on the strength of the ligand field. It is obvious that this effect of tautomeric forms of thioamides is associated with the formation of a conjugate system of double bonds in their molecules. In this case, the transition of thioamide to thiol form depends on the pH and the nature of the organic solvent: in a weakly alkaline medium or polar organic solvent (pyridine, chloroform) there is a shift of equilibrium towards to the dominance of thiol tautomeric form. It was found that the thionic tautomeric form of thioamides (depending on pH and substituent composition) reacts with metal salts mainly in neutral form or in the monoanionic form, forming complexes of molecular or ionic nature, while thiol form reacts in the form of dianion, forming complexes preferably anionic type. Ionic compounds are usually soluble or sparingly soluble in water in low concentrations (10-3–10-5 mol/l), while compounds of the molecular type are soluble only in DMSO and DMF. It is shown that the stereoselective synthesis of various ligand complexes is carried out mainly in three ways: 1) by the interaction of the initial components in the corresponding stoichiometry. In this case, the vacancy in the metal environment is occupied by either the anions of the starting metal salt (Hal-, SO42-, NO3-, CH3COO-, etc.) or other organic molecules (triphenylphosphine, pyridine, etc.); 2) carrying out parallel reactions (hydrolysis and oxidation of thioureas), which lead to participation in the coordination of by-p
竞争配位、功能取代硫酰胺的互变异构体形式、合成条件和金属性质对三维和4d金属的单核、双核和多核配合物的反应过程和结构的影响是根据乌克兰国家科学院维尔纳德斯基普通化学和无机化学研究所"复杂化合物化学"系取得的结果考虑的。与乌克兰国家科学院有机化学研究所“杂环化合物化学”部门的工作人员一起。基于d金属与功能取代N, S-和O, N, S-含硫酰胺的反应，研究了配体密度以及络合物形成条件对所得到的配合物结构及其多态修饰的影响。此外，还证明了硫酰胺互变异构体形式对配位多面体立体化学的影响:发现在配合物结构中，硫离子互变异构体形式促进硫脲的转位，而巯基形式促进其在三维、四维金属多面体的正方形平面上的顺式位置。然而，研究发现，硫离子互变异构体形式导致八面体的形成，而硫醇形式导致Cu(II)和Ni(II)配合物中配位节点的方平面，其特征是配位多面体的变化(从方平面和四面体到八面体)取决于配体场的强度。很明显，硫酰胺互变异构体的这种作用与其分子中双键共轭体系的形成有关。在这种情况下，硫酰胺向硫醇形式的转变取决于pH值和有机溶剂的性质:在弱碱性介质或极性有机溶剂(吡啶，氯仿)中，平衡向硫醇互变异构体形式的主导地位转变。硫胺的硫离子互变异构体形式(取决于pH值和取代基组成)与金属盐主要以中性形式或单阴离子形式反应，形成分子或离子性质的配合物，而硫醇形式以阴离子形式反应，形成阴离子类型的配合物。离子型化合物通常在低浓度(10-3-10-5 mol/l)的水中可溶或微溶，而分子型化合物只溶于DMSO和DMF。结果表明，各种配体配合物的立体选择性合成主要通过三种方式进行:1)通过相应化学计量中初始组分的相互作用。在这种情况下，金属环境中的空位要么被起始金属盐的阴离子(Hal-、SO42-、NO3-、CH3COO-等)占据，要么被其他有机分子(三苯基膦、吡啶等)占据;2)进行平行反应(硫脲的水解和氧化)，从而参与反应副产物的配位;3)与配体内重排进行反应，导致有机配体的环化及其转化为中心金属离子的产物的配位。然而，研究发现取代多齿硫胺在合成条件和配合金属作为有机反应促进剂的作用下均可发生水解/氧化或配体内环化。研究发现，根据起始试剂相互作用的温度和时间，可以形成不同的多态修饰物(三斜或单斜)，其堆积密度和分子间相互作用的性质不同。因此，这些多态修饰在水中具有不同的溶解度，这对控制合成合适的结构及其实际应用具有重要意义。
{"title":"FUNDAMENTAL ASPECTS OF THE COORDINATION CHEMISTRY OF TRANSITION METALS WITH FUNCTIONALLY SUBSTITUTED THIOAMIDES (PART 1)","authors":"S. Orysyk, V. Pekhnyo, V. Orysyk, Yu. L. Zborovskii, P. Borovyk, V. Mykhailo","doi":"10.33609/2708-129x.88.02.2022.85-115","DOIUrl":"https://doi.org/10.33609/2708-129x.88.02.2022.85-115","url":null,"abstract":"The influence of competitive coordination, a tautomeric form of functionally substituted thioamides, conditions of synthesis and nature of the metal on the course of the reaction and structure of mono-, bi, and polynuclear complexes of 3d, 4d-metals is considered based on results obtained in the Department of \"Chemistry of Complex Compounds\" of the V.I. Vernadsky Institute of General and Inorganic Chemistry NAS of Ukraine, together with the staff of the Department of “Chemistry of Heterocyclic Compounds” of the Institute of Organic Chemistry NAS of Ukraine. \u0000The influence of ligand denticity, as well as conditions of complex formation on the structure of obtained complexes and their polymorphic modifications, was studied based on the reaction of d-metals with functionally substituted N, S- and O, N, S-containing thioamides. In addition, it is proved the influence of tautomeric forms of thioamides on the stereochemistry of coordination polyhedra: it is found that the thionic tautomeric form promotes the transposition of thioureas, while the thiol form promotes its cis-position in the square-planar of a polyhedron of 3d, 4d-metals in the structure of complexes. However, it was found that the thion tautomeric form leads to the formation of octahedral, while the thiol form to the square-planar of coordination nodes in complexes of Cu(II) and Ni(II), which are characterized by a change in coordination polyhedra (from square-planar and tetrahedron to octahedron) that depending on the strength of the ligand field. It is obvious that this effect of tautomeric forms of thioamides is associated with the formation of a conjugate system of double bonds in their molecules. In this case, the transition of thioamide to thiol form depends on the pH and the nature of the organic solvent: in a weakly alkaline medium or polar organic solvent (pyridine, chloroform) there is a shift of equilibrium towards to the dominance of thiol tautomeric form. \u0000It was found that the thionic tautomeric form of thioamides (depending on pH and substituent composition) reacts with metal salts mainly in neutral form or in the monoanionic form, forming complexes of molecular or ionic nature, while thiol form reacts in the form of dianion, forming complexes preferably anionic type. Ionic compounds are usually soluble or sparingly soluble in water in low concentrations (10-3–10-5 mol/l), while compounds of the molecular type are soluble only in DMSO and DMF. \u0000It is shown that the stereoselective synthesis of various ligand complexes is carried out mainly in three ways: 1) by the interaction of the initial components in the corresponding stoichiometry. In this case, the vacancy in the metal environment is occupied by either the anions of the starting metal salt (Hal-, SO42-, NO3-, CH3COO-, etc.) or other organic molecules (triphenylphosphine, pyridine, etc.); 2) carrying out parallel reactions (hydrolysis and oxidation of thioureas), which lead to participation in the coordination of by-p","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91108129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-03-25DOI: 10.33609/2708-129x.88.02.2022.116-130
E. Trunova, A. Mishchenko, T. Makotryk
New heterometallic complexes of Nd(III) and Co(II) based on ethylenediaminetetraacetic and ethylenediaminedisuccinic acids have been synthesized. The complexes studied by electron absorption spectroscopy, IR-spectroscopy, and thermogravimetric analysis. The influence of a number of factors on the properties and structure of heteronuclear complexes is discussed. The spectral characteristics of homonuclear and heteronuclear complexes are compared. A theoretical analysis of the geometry of Co(II) and Nd(III) complexes with ethylenediaminesuccinic acid was carried out by the semi-empirical PM7 method. It has been shown that the f-d-complexes are of the folded type, in which the ligand-complexone realizes the maximum denticity to Nd(III), and the Co(II) coordination sphere is formed by bridging edta/edds carboxyl groups and intrasphere water molecules. The Co(II) coordination polyhedron corresponds to a distorted octahedron, and the Nd(III) coordination polyhedron corresponds to a one-capped square antiprism (C4v) with the coordination number Nd(III)=8. During study fixed that heterometallic complexes have the same structure in solutions and in the solid state.
{"title":"SYNTHESIS, SPECTRAL CHARACTERIZATION AND STABILITY OF THE NEW ND (III) AND CO (II) HETEROMETALLIC COMPLEXES WITH AMINOPOLYCARBOXYLIC ACIDS","authors":"E. Trunova, A. Mishchenko, T. Makotryk","doi":"10.33609/2708-129x.88.02.2022.116-130","DOIUrl":"https://doi.org/10.33609/2708-129x.88.02.2022.116-130","url":null,"abstract":"New heterometallic complexes of Nd(III) and Co(II) based on ethylenediaminetetraacetic and ethylenediaminedisuccinic acids have been synthesized. The complexes studied by electron absorption spectroscopy, IR-spectroscopy, and thermogravimetric analysis. The influence of a number of factors on the properties and structure of heteronuclear complexes is discussed. The spectral characteristics of homonuclear and heteronuclear complexes are compared. A theoretical analysis of the geometry of Co(II) and Nd(III) complexes with ethylenediaminesuccinic acid was carried out by the semi-empirical PM7 method. It has been shown that the f-d-complexes are of the folded type, in which the ligand-complexone realizes the maximum denticity to Nd(III), and the Co(II) coordination sphere is formed by bridging edta/edds carboxyl groups and intrasphere water molecules. The Co(II) coordination polyhedron corresponds to a distorted octahedron, and the Nd(III) coordination polyhedron corresponds to a one-capped square antiprism (C4v) with the coordination number Nd(III)=8. During study fixed that heterometallic complexes have the same structure in solutions and in the solid state.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73508307","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-03-25DOI: 10.33609/2708-129x.88.02.2022.131-137
Mykola Koshel, S. Koshel, Y. Polishchuk
A mathematical model of mass transfer processes in the electrolysis of one-component solutions of 1,1 symmetric strong electrolytes NaOH and NaCl in a two-chamber electrochemical reactor with mesh electrodes based on platinum titanium is formulated. Experimental modeling of processes is performed was carried out under conditions of continuous precise monitoring of the system (NaOH concentration and volume of solution in the chambers).The electrolysis system was designed to balance the flow of components through the membrane to study its properties and to determine five unknown parameters of mathematical modeling of the process. The mathematical model is a system of equations, which includes the unknown transfer numbers of counterions through the membrane, the electrolyte diffusion coefficient, the electroosmotic flux constant, and the empirical parameters of the approximating expressions.
{"title":"MATHEMATICAL MODEL OF TWO-CHAMBER ELECTROLYSER DYNAMICS FOR STUDYING PROPERTIES OF ION EXCHANGE MEMBRANES BASED ON PROTON IONIC LIQUIDS","authors":"Mykola Koshel, S. Koshel, Y. Polishchuk","doi":"10.33609/2708-129x.88.02.2022.131-137","DOIUrl":"https://doi.org/10.33609/2708-129x.88.02.2022.131-137","url":null,"abstract":"A mathematical model of mass transfer processes in the electrolysis of one-component solutions of 1,1 symmetric strong electrolytes NaOH and NaCl in a two-chamber electrochemical reactor with mesh electrodes based on platinum titanium is formulated. Experimental modeling of processes is performed was carried out under conditions of continuous precise monitoring of the system (NaOH concentration and volume of solution in the chambers).The electrolysis system was designed to balance the flow of components through the membrane to study its properties and to determine five unknown parameters of mathematical modeling of the process. The mathematical model is a system of equations, which includes the unknown transfer numbers of counterions through the membrane, the electrolyte diffusion coefficient, the electroosmotic flux constant, and the empirical parameters of the approximating expressions.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90628007","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-03-25DOI: 10.33609/2708-129x.88.02.2022.138-146
V. Kozin, A. Bliznyuk
Thanks to the unique combination of physicochemical properties, metal hydrides (MH) are widely used in various fields of science and technology. High thermal, chemical and radiation resistance MH allows it to be used in nuclear industry as a material for nuclear reactors, chemical engineering, metallurgy for the production and refining of metals, for the production of devices operating at elevated temperatures and in adverse conditions. Unique properties MH are widely used in hydrogen energy as hydrogen storage, in rechargeable batteries. Analysis of literature data has shown that most studies are devoted to the practical use of the unique MH ability of reversibly absorbs a large amount of hydrogen. However, the electrochemical characteristics of the electrode processes of metal hydride systems were practically not investigated. The aim of this work is to study the processes that take place on the titanium electrode in sulfuric acid solutions, and the composition of titanium compounds that are formed. The paper presents the results of studies of the hydride formation reactions occurring on a polarized titanium cathode in aqueous solution 2 N sulfuric acid. The study was carried out using the following methods: the cyclic voltammetry and the method of x-ray phase analysis of the composition of the surface. It has been found that the reduction of hydrogen at the titanium cathode from a solution of sulfuric acid is accompanied by the formation of hydrides, which causes an increase in the overvoltage of hydrogen evolution and high values of the angular coefficients of the Tafel dependence. The kinetic parameters of this process have been calculated: the transfer coefficients α, theoretical and experimental angular coefficients btheor and bexp , exchange currents ie, the dependence of the hydrogen overvoltage from temperature. It has been found that exchange current density of hydrogen evolution reaction in this system is close by value to the current exchange of hydrogen evolution at the noble metals Pd, Pt, Rh, Ir and are (2,70∙÷0,8)∙10-3А·sm-2 in the temperature range 298 ÷ 343 K. The value of activation energy of 19,83 kJ mol-1 indicates the diffusion control of this process.
{"title":"HYDROGEN’S EVOLUTION ON TITANIUM ELECTRODE FROM SULFURIC ACID SOLUTION","authors":"V. Kozin, A. Bliznyuk","doi":"10.33609/2708-129x.88.02.2022.138-146","DOIUrl":"https://doi.org/10.33609/2708-129x.88.02.2022.138-146","url":null,"abstract":"Thanks to the unique combination of physicochemical properties, metal hydrides (MH) are widely used in various fields of science and technology. High thermal, chemical and radiation resistance MH allows it to be used in nuclear industry as a material for nuclear reactors, chemical engineering, metallurgy for the production and refining of metals, for the production of devices operating at elevated temperatures and in adverse conditions. Unique properties MH are widely used in hydrogen energy as hydrogen storage, in rechargeable batteries. Analysis of literature data has shown that most studies are devoted to the practical use of the unique MH ability of reversibly absorbs a large amount of hydrogen. However, the electrochemical characteristics of the electrode processes of metal hydride systems were practically not investigated. \u0000The aim of this work is to study the processes that take place on the titanium electrode in sulfuric acid solutions, and the composition of titanium compounds that are formed. The paper presents the results of studies of the hydride formation reactions occurring on a polarized titanium cathode in aqueous solution 2 N sulfuric acid. The study was carried out using the following methods: the cyclic voltammetry and the method of x-ray phase analysis of the composition of the surface. It has been found that the reduction of hydrogen at the titanium cathode from a solution of sulfuric acid is accompanied by the formation of hydrides, which causes an increase in the overvoltage of hydrogen evolution and high values of the angular coefficients of the Tafel dependence. The kinetic parameters of this process have been calculated: the transfer coefficients α, theoretical and experimental angular coefficients btheor and bexp , exchange currents ie, the dependence of the hydrogen overvoltage from temperature. It has been found that exchange current density of hydrogen evolution reaction in this system is close by value to the current exchange of hydrogen evolution at the noble metals Pd, Pt, Rh, Ir and are (2,70∙÷0,8)∙10-3А·sm-2 in the temperature range 298 ÷ 343 K. The value of activation energy of 19,83 kJ mol-1 indicates the diffusion control of this process.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80772643","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-02-16DOI: 10.33609/2708-129x.88.01.2022.67-81
V. Saberov, Alexandr S. Avksentiev, G. Rayenko, A. Ryabitsky, Vasil I. Yenya, Maxim Nechitaylov, N. Korotkikh
The synthesis of a number of carbene PEPPSI-complexes of palladium with various pyridine and carbene ligands was carried out by reactions of 1,3-bis-(2,6-dibenzhydryl-4-methylphenyl)imidazolium chloride IPr*.HCl [compounds 7a-c IPr*PdCl2L’, L’ = pyridine (а), 3-chloropyridine (b), 4-dimethylaminopyridine (с)], 1,3-bis-(2,6-diisopropylphenyl)imidazolium perchlorate IPr.HClO4 [compounds 8a,b IPr.PdCl2L’, L’ = 3-chloropyridine (а), о-phenanthroline (b)], 1,3-diphenyl-4-(2,6-diisopropylphenyl)-1,2,4-triazolium perchlorate L.HClO4 (complex 9 LPdCl2L’, L’ = 3-chloropyridine) and 1,3-dicetylimidazolium bromide L.HBr (complex 11 LPdCl2L’, L’ = pyridine) with palladium chloride in pyridines (pyridine, 3-chloropyridine), or acetonitrile in the presence of potassium carbonate. Yields of compounds – from high (56–100%) to moderate (36 %). The structure of the compounds was confirmed by 1H and 13C NMR spectroscopy. Chemical shifts of carbene atoms in the 13C NMR spectra of complexes 7a-c. 8a, b 11 are in the region 151.0-156.2 ppm, for complex 9 - at 174.4 ppm A high catalytic effect of sterically shielded complexes 7a, b, 8a, b in the hydrodehalogenation reaction of p-dichlorobenzene and hexachlorobenzene under the action of potassium tert-butoxide in isopropanol was established. 1,3-Bis-(2,6-dibenzhydryl-4-methylphenyl)-imidazol-2-ylidene complexes 7a, b (quantitative conversions with p-dichlorobenzene are achieved with 0.013 mol% of catalyst) show the highest efficiency, but the compound with 4-dimethylaminopyridine ligand 7c has significantly lower efficiency (22% conversion under these conditions). Complexes with 1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene ligand 8a, b are close in efficiency to compounds 7a, b (for 7a quantitative conversion is achieved with 0.026 mol% of catalyst). Phenanthroline-containing complex 8b is less effective than complex 8a (87% conversion with 0.052 mol% of catalyst). Complex 9 is much less effective (even with 0.13 mol% of catalyst 13% conversion is achieved). Compound 11 catalyzes the reaction well only when the amount of catalyst is up to 1.3 mol% (98% conversion). Thus, compounds 7a, b, 8a are the best PEPPSI-catalysts for hydrodehalogenation of haloarenes promising for industrial decontamination of persistent organic pollutants (hexachlorobenzene, DDT, dioxins and polychlorinated biphenyls, etc.).
{"title":"CATALYSIS OF HYDRODEHALOGENATION REACTION OF HALOARENES BY CARBENE PEPPSI-PALLADIUM COMPLEXES","authors":"V. Saberov, Alexandr S. Avksentiev, G. Rayenko, A. Ryabitsky, Vasil I. Yenya, Maxim Nechitaylov, N. Korotkikh","doi":"10.33609/2708-129x.88.01.2022.67-81","DOIUrl":"https://doi.org/10.33609/2708-129x.88.01.2022.67-81","url":null,"abstract":"The synthesis of a number of carbene PEPPSI-complexes of palladium with various pyridine and carbene ligands was carried out by reactions of 1,3-bis-(2,6-dibenzhydryl-4-methylphenyl)imidazolium chloride IPr*.HCl [compounds 7a-c IPr*PdCl2L’, L’ = pyridine (а), 3-chloropyridine (b), 4-dimethylaminopyridine (с)], 1,3-bis-(2,6-diisopropylphenyl)imidazolium perchlorate IPr.HClO4 [compounds 8a,b IPr.PdCl2L’, L’ = 3-chloropyridine (а), о-phenanthroline (b)], 1,3-diphenyl-4-(2,6-diisopropylphenyl)-1,2,4-triazolium perchlorate L.HClO4 (complex 9 LPdCl2L’, L’ = 3-chloropyridine) and 1,3-dicetylimidazolium bromide L.HBr (complex 11 LPdCl2L’, L’ = pyridine) with palladium chloride in pyridines (pyridine, 3-chloropyridine), or acetonitrile in the presence of potassium carbonate. Yields of compounds – from high (56–100%) to moderate (36 %). The structure of the compounds was confirmed by 1H and 13C NMR spectroscopy. Chemical shifts of carbene atoms in the 13C NMR spectra of complexes 7a-c. 8a, b 11 are in the region 151.0-156.2 ppm, for complex 9 - at 174.4 ppm A high catalytic effect of sterically shielded complexes 7a, b, 8a, b in the hydrodehalogenation reaction of p-dichlorobenzene and hexachlorobenzene under the action of potassium tert-butoxide in isopropanol was established. 1,3-Bis-(2,6-dibenzhydryl-4-methylphenyl)-imidazol-2-ylidene complexes 7a, b (quantitative conversions with p-dichlorobenzene are achieved with 0.013 mol% of catalyst) show the highest efficiency, but the compound with 4-dimethylaminopyridine ligand 7c has significantly lower efficiency (22% conversion under these conditions). Complexes with 1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene ligand 8a, b are close in efficiency to compounds 7a, b (for 7a quantitative conversion is achieved with 0.026 mol% of catalyst). Phenanthroline-containing complex 8b is less effective than complex 8a (87% conversion with 0.052 mol% of catalyst). Complex 9 is much less effective (even with 0.13 mol% of catalyst 13% conversion is achieved). Compound 11 catalyzes the reaction well only when the amount of catalyst is up to 1.3 mol% (98% conversion). Thus, compounds 7a, b, 8a are the best PEPPSI-catalysts for hydrodehalogenation of haloarenes promising for industrial decontamination of persistent organic pollutants (hexachlorobenzene, DDT, dioxins and polychlorinated biphenyls, etc.).","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88630474","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-02-16DOI: 10.33609/2708-129x.88.01.2022.3-22
O. Kozachkova, Nataliya Tsaryk, V. Pekhnyo, V. Trachevskij
The complexation of cis-Pd(NH3)2Cl2 and Pd(en)Cl2 (en – ethylenediamine) with 1-aminopropylidene-1,1-diphosphonic acid (APrDP, H4L) in solutions with extracellular concentration of chloride ions (0.15 mol/L) at the rations Pd(II):APrDP=1:1, 1:2 and 2:1 has been studied by pH-potentiometry, electron and NMR spectroscopy. It has been found that upon interaction in the system cis-Pd(NH3)2Cl2:AprDP=1:1, complexes of the equimolar composition [PdHL(NH3)Cl]2- (lgβ=38.84(4)), [PdHL(NH3)2]- (lgβ=43.14(2)) and [PdL(NH3)2]2- (lgβ=34.91(2)) are formed depending on pH, in which the APrDP molecule is coordinated in a bidentate fashion to the central ion by the nitrogen atom of the amine group and oxygen atom of the phosphonic group. In the case of twofold excess of ligand, bisligand complexes [PdH4L2]2- (lgβ=59.64(9)), [PdH3L2]3- (lgβ=57.39(19), [PdH2L2]4- (lgβ=52.37(17), [PdHL2]5- (lgβ=44.71(9)) [PdL2]6- (lgβ=36.57(6)) are formed, in which two APrDP molecules are coordinated in a bidentated fashion. At pH>6, complexes [PdHL2(NH3)]5- (lgβ=48.57(6)) and [PdL2(NH3)2]6- (lgβ=42.76(8)) are formed, in which the coordinated phosphonic groups of APrDP are sequentially replaced upon coordination by NH3. molecules. In the systems Pd(en)Cl2:APrDP=1:1 and 1:2, complexes only of equimolar composition: [Pd(en)(H2L)] (lgβ=28.88(9)), [Pd(en)(HL)]- (lgβ=24.67(8)) and [Pd(en)L]2- (lgβ=16.84(9)) are formed, whose coordination sphere contains the nitrogen atom of the amine group and oxygen atom of the phosphonic group of APrDP and two nitrogen atoms of the amine groups of an ethylenediamine. At the ratio Pd(II):APrDP=2:1, the formation of binuclear complexes {[Pd(NH3)2]2L} (lgβ=63.58(22)) and {[Pd(en)]2L} (lgβ= 25.18(4)), in which two palladium atoms have a different coordination environment. The coordination sphere of one of the palladium contains a nitrogen atom of the amine group and an oxygen atom of the phosphonic group of APrDP, and two NH3 molecules or two amine groups of ethylenediamine. The other palladium coordinates two oxygen atoms of phoshonic groups of APrDP and two NH3 molecules or two amine groups of ethylenediamine.
{"title":"COMPLEXATION OF CIS-Pd(NH3)2Cl2 AND Pd(en)Cl2 WITH 1-AMINOPROPYLIDENEDIPHOSPHONIC ACID","authors":"O. Kozachkova, Nataliya Tsaryk, V. Pekhnyo, V. Trachevskij","doi":"10.33609/2708-129x.88.01.2022.3-22","DOIUrl":"https://doi.org/10.33609/2708-129x.88.01.2022.3-22","url":null,"abstract":"The complexation of cis-Pd(NH3)2Cl2 and Pd(en)Cl2 (en – ethylenediamine) with 1-aminopropylidene-1,1-diphosphonic acid (APrDP, H4L) in solutions with extracellular concentration of chloride ions (0.15 mol/L) at the rations Pd(II):APrDP=1:1, 1:2 and 2:1 has been studied by pH-potentiometry, electron and NMR spectroscopy. \u0000It has been found that upon interaction in the system cis-Pd(NH3)2Cl2:AprDP=1:1, complexes of the equimolar composition [PdHL(NH3)Cl]2- (lgβ=38.84(4)), [PdHL(NH3)2]- (lgβ=43.14(2)) and [PdL(NH3)2]2- (lgβ=34.91(2)) are formed depending on pH, in which the APrDP molecule is coordinated in a bidentate fashion to the central ion by the nitrogen atom of the amine group and oxygen atom of the phosphonic group. In the case of twofold excess of ligand, bisligand complexes [PdH4L2]2- (lgβ=59.64(9)), [PdH3L2]3- (lgβ=57.39(19), [PdH2L2]4- (lgβ=52.37(17), [PdHL2]5- (lgβ=44.71(9)) [PdL2]6- (lgβ=36.57(6)) are formed, in which two APrDP molecules are coordinated in a bidentated fashion. At pH>6, complexes [PdHL2(NH3)]5- (lgβ=48.57(6)) and [PdL2(NH3)2]6- (lgβ=42.76(8)) are formed, in which the coordinated phosphonic groups of APrDP are sequentially replaced upon coordination by NH3. molecules. \u0000In the systems Pd(en)Cl2:APrDP=1:1 and 1:2, complexes only of equimolar composition: [Pd(en)(H2L)] (lgβ=28.88(9)), [Pd(en)(HL)]- (lgβ=24.67(8)) and [Pd(en)L]2- (lgβ=16.84(9)) are formed, whose coordination sphere contains the nitrogen atom of the amine group and oxygen atom of the phosphonic group of APrDP and two nitrogen atoms of the amine groups of an ethylenediamine. \u0000At the ratio Pd(II):APrDP=2:1, the formation of binuclear complexes {[Pd(NH3)2]2L} (lgβ=63.58(22)) and {[Pd(en)]2L} (lgβ= 25.18(4)), in which two palladium atoms have a different coordination environment. The coordination sphere of one of the palladium contains a nitrogen atom of the amine group and an oxygen atom of the phosphonic group of APrDP, and two NH3 molecules or two amine groups of ethylenediamine. The other palladium coordinates two oxygen atoms of phoshonic groups of APrDP and two NH3 molecules or two amine groups of ethylenediamine.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87795726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-02-16DOI: 10.33609/2708-129x.88.01.2022.49-66
L. Kobrina, V. Boyko, Halyna Hliieva, S. Riabov, S. Rogalsky, K. Yanova
The inclusion complexation of sulfobutyl ether-β-cyclodextrin sodium salt (SBECD) - ionic liquid (IL) has been investigated by a series of appropriate methods. The stability constant of the complex of SBECD-IL (K = 72.4 m-1) was determined by the method of Higuchi and Connors. An increase in the surface tension of solutions with different SBECD’s content was recorded by using the method of Wilhelm's plate, which could serve as an additional evidence of the formation of inclusion complex between SBECD and IL. Analysis of the TGA results provided for the initial IL and SBECD, their mechanical mixture and the complex elaborated allows us to conclude that the "guest-host" type complexation is emerged. Differential scanning calorimetry (DSC) data also confirmed the formation of inclusion complex between SBECD and IL. While the guest molecule is incorporated into cyclodextrin cavity, its thermal properties are changed. So, the loss of physically bonded water in the complex is equal to 5% by weight, indicating the IL’s molecule being located in the SBECD’s hydrophobic cavity. The thermogram of inclusion complex demonstrates just one endothermic peak at 74 oC. The complex is formed by entering the long alkyl chain of ionic liquid into the hydrophobic cavity of SBECD. Since the bonds of sulfo groups and β-СD’s glucopyran cycles become weaker, this may testify an additional interactions between SBECD and IL. With thermograviometric analysis (TGA) of the original IR and SB-β-CD, their mechanical mixture and the test compound fixed the formation of not a classical complex, but an associated complex of inclusion type "guest-host", which is formed by entering a long alkyl chain IR in the hydrophobic cavity SB-β-CD.
{"title":"PECULIARITIES OF COMPLEX FORMATION IN THE SULFOBUTYL ETHER-β-CYCLODEXTRIN - IONIC LIQUID SYSTEM","authors":"L. Kobrina, V. Boyko, Halyna Hliieva, S. Riabov, S. Rogalsky, K. Yanova","doi":"10.33609/2708-129x.88.01.2022.49-66","DOIUrl":"https://doi.org/10.33609/2708-129x.88.01.2022.49-66","url":null,"abstract":"The inclusion complexation of sulfobutyl ether-β-cyclodextrin sodium salt (SBECD) - ionic liquid (IL) has been investigated by a series of appropriate methods. The stability constant of the complex of SBECD-IL (K = 72.4 m-1) was determined by the method of Higuchi and Connors. An increase in the surface tension of solutions with different SBECD’s content was recorded by using the method of Wilhelm's plate, which could serve as an additional evidence of the formation of inclusion complex between SBECD and IL. Analysis of the TGA results provided for the initial IL and SBECD, their mechanical mixture and the complex elaborated allows us to conclude that the \"guest-host\" type complexation is emerged. Differential scanning calorimetry (DSC) data also confirmed the formation of inclusion complex between SBECD and IL. While the guest molecule is incorporated into cyclodextrin cavity, its thermal properties are changed. So, the loss of physically bonded water in the complex is equal to 5% by weight, indicating the IL’s molecule being located in the SBECD’s hydrophobic cavity. The thermogram of inclusion complex demonstrates just one endothermic peak at 74 oC. The complex is formed by entering the long alkyl chain of ionic liquid into the hydrophobic cavity of SBECD. Since the bonds of sulfo groups and β-СD’s glucopyran cycles become weaker, this may testify an additional interactions between SBECD and IL. With thermograviometric analysis (TGA) of the original IR and SB-β-CD, their mechanical mixture and the test compound fixed the formation of not a classical complex, but an associated complex of inclusion type \"guest-host\", which is formed by entering a long alkyl chain IR in the hydrophobic cavity SB-β-CD.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78883155","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-02-16DOI: 10.33609/2708-129x.88.01.2022.23-34
A. Shumeiko
The reactions of phenolysis of cyclophosphazenes, leading to the formation of monoaryl oxide derivatives with an excess of the substrate, were studied. The interest in this reaction is dictated by the practical value of the reaction products, which are easily formed under the conditions of transphase catalysis, and also by the fact that the studied regularities of phenolysis can extend to a significant spectrum of transphase nucleophilic substitution reactions. The general regularities of the transphase reaction of phosphazenes phenolysis were established by the example of the interaction of 4-nitrophenol with a phosphornitrile chloride trimer in a two-phase system. It was shown that the topology of the transphase chemical interaction is influenced by the same factors as the limiting stage, and therefore, by varying the ratio of lipophilicity and nucleophilicity of the transphase reagent, one can purposefully change the place of its interaction with the substrate. It was shown that the phenolysis of cyclotriphosphazenes occurs in the bulk of the organic phase or, alternatively, in the organic sublayer adjacent to the phase separation boundary. The presented data suggested that the transphase reaction can be described in terms of a single mechanism, in contrast to the generally accepted division into extraction and phase transfer. Thus, the topology of the transphase chemical interaction is influenced by the same factors as the limiting stage, and therefore, by varying the ratio of lipophilicity and nucleophilicity of transphase reagents, one can purposefully change the zone of their interaction with the substrate. In this case, the rate of the homogeneous response and the hydrophilicity of the ionic agent must be taken into account. The features of the transphase reaction described here can be extended to other catalysts, such as betaines, the analogs of which have been used in various reactions of a similar type.
{"title":"STEREOSELECTIVITY IN THE REACTIONS OF PHENOLYSIS OF CYCLIC PHOSPHASENES UNDER CONDITIONS OF TRANSPHASE CATALYSIS","authors":"A. Shumeiko","doi":"10.33609/2708-129x.88.01.2022.23-34","DOIUrl":"https://doi.org/10.33609/2708-129x.88.01.2022.23-34","url":null,"abstract":"The reactions of phenolysis of cyclophosphazenes, leading to the formation of monoaryl oxide derivatives with an excess of the substrate, were studied. The interest in this reaction is dictated by the practical value of the reaction products, which are easily formed under the conditions of transphase catalysis, and also by the fact that the studied regularities of phenolysis can extend to a significant spectrum of transphase nucleophilic substitution reactions. The general regularities of the transphase reaction of phosphazenes phenolysis were established by the example of the interaction of 4-nitrophenol with a phosphornitrile chloride trimer in a two-phase system. It was shown that the topology of the transphase chemical interaction is influenced by the same factors as the limiting stage, and therefore, by varying the ratio of lipophilicity and nucleophilicity of the transphase reagent, one can purposefully change the place of its interaction with the substrate. It was shown that the phenolysis of cyclotriphosphazenes occurs in the bulk of the organic phase or, alternatively, in the organic sublayer adjacent to the phase separation boundary. The presented data suggested that the transphase reaction can be described in terms of a single mechanism, in contrast to the generally accepted division into extraction and phase transfer. Thus, the topology of the transphase chemical interaction is influenced by the same factors as the limiting stage, and therefore, by varying the ratio of lipophilicity and nucleophilicity of transphase reagents, one can purposefully change the zone of their interaction with the substrate. In this case, the rate of the homogeneous response and the hydrophilicity of the ionic agent must be taken into account. The features of the transphase reaction described here can be extended to other catalysts, such as betaines, the analogs of which have been used in various reactions of a similar type.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73109846","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-02-16DOI: 10.33609/2708-129x.88.01.2022.35-48
R. Khoma, A. Ennan, T. Bienkovska, R. Dlubovskii, S. Vodzinskii, T. Mykhailova
The paper presents the research results on the colorimetric behavior of impregnated fibrous chemisorbents (IFCS-I) of acid gases with visual identification of the dynamic absorption capacity “response” moment during the absorption of sulfur dioxide. Chemisorbents were obtained by impregnation of fibrous carriers by N-containing organic bases aqueous solutions with adding acid-base indicators (Ind). IFCS-I based on hexamethylenetetramine (IFCS-HMTA-I) and polyethylenepolyamine (IFCS-PEPA-I), as well as IFCS-MEA-EDTA-I based on monoethanolamine (MEA) and the disodium salt of ethylenediaminetetraacetic acid (EDTA) were used. The change specificity of colorimetric functions of indicator impregnated fibrous chemisorbents during their absorption of SO2 is revealed. IFCS-I original samples color significantly depends not only on the structure of Ind, but also the nature of amines (MEA, HMTA and PEPA), which are part of them. The color of the “response” samples of IFCS-MEA-EDTA-I, IFCS-PEPA-I and IFCS-HMTA-I, differ from the same properties of Bronsted acids aqueous solutions. The color change of azo-indicators occurs due to redox reactions with sulfite compounds. PEPA molecules and their ammonium cations in the composition of IFCS-I stabilize azo-indicators to these redox transformations.
{"title":"THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE","authors":"R. Khoma, A. Ennan, T. Bienkovska, R. Dlubovskii, S. Vodzinskii, T. Mykhailova","doi":"10.33609/2708-129x.88.01.2022.35-48","DOIUrl":"https://doi.org/10.33609/2708-129x.88.01.2022.35-48","url":null,"abstract":"The paper presents the research results on the colorimetric behavior of impregnated fibrous chemisorbents (IFCS-I) of acid gases with visual identification of the dynamic absorption capacity “response” moment during the absorption of sulfur dioxide. Chemisorbents were obtained by impregnation of fibrous carriers by N-containing organic bases aqueous solutions with adding acid-base indicators (Ind). IFCS-I based on hexamethylenetetramine (IFCS-HMTA-I) and polyethylenepolyamine (IFCS-PEPA-I), as well as IFCS-MEA-EDTA-I based on monoethanolamine (MEA) and the disodium salt of ethylenediaminetetraacetic acid (EDTA) were used. The change specificity of colorimetric functions of indicator impregnated fibrous chemisorbents during their absorption of SO2 is revealed. IFCS-I original samples color significantly depends not only on the structure of Ind, but also the nature of amines (MEA, HMTA and PEPA), which are part of them. The color of the “response” samples of IFCS-MEA-EDTA-I, IFCS-PEPA-I and IFCS-HMTA-I, differ from the same properties of Bronsted acids aqueous solutions. The color change of azo-indicators occurs due to redox reactions with sulfite compounds. PEPA molecules and their ammonium cations in the composition of IFCS-I stabilize azo-indicators to these redox transformations.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75234200","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2022-01-21DOI: 10.33609/2708-129x.87.12.2021.121-136
Volodymyr Trachevskiy, S. Prudius, A. Mylin
The study is devoted to the solution of one of the actual problems of materials science – the conscious management of the fundamental properties of solids. It is based on the development of an algorithm for creating both on intergranular surfaces and in the volume of particles nanosized inclusions, crystallites, structural defects. Taking into account the accumulated results of systematic studies of simple, binary systems as previous experience for further design of more complex systems, for correctly overcome the fundamental disadvantages, associated with the inconsistency of multicomponent systems, the sequence of physico-chemically substantiated technological stages on the way of formation of functional architecture has been formulated. The coevolutionary concept of self-organization of chemical systems is also formulated, according to which the regulation of the course of structural-functional reorganization processes takes place by two mechanisms: adaptation and bifurcation. Taking into account the physicochemical properties, optimal conditions for the formation of element oxide clusters and the peculiarities of interparticle interaction, the course of structural and functional self-organization – response of colloidal solutions of a multicomponent system to directionally initiated changes in the characteristics of the dispersed reaction medium and, accordingly, the parameters of particles that are deliberately designed in this way (size, shape, composition, structure of their ensembles), as well as the effect on interparticle distances, hierarchy of structural levels, the action of concentration and temperature factors and the introduction of a modifying reagent were diagnosed by various measurements. The driving forces (electronegativity, competitive rearrangements) and tendencies of energy-supplied bifurcation formation of coordination polyhedra of structure-forming ions in multicomponent ensembles were identified, namely, the pathways of directed initiated rearrangement of the atomic architecture with the organization of oxygen-unsaturated zirconium-containing sites, which determined the matrix formation with practically significant catalytic activity.
{"title":"STRUCTURE-FUNCTIONAL SELF-ORGANIZATION OF ZrO2–SiO2:Sn(IV) SYSTEM","authors":"Volodymyr Trachevskiy, S. Prudius, A. Mylin","doi":"10.33609/2708-129x.87.12.2021.121-136","DOIUrl":"https://doi.org/10.33609/2708-129x.87.12.2021.121-136","url":null,"abstract":"The study is devoted to the solution of one of the actual problems of materials science – the conscious management of the fundamental properties of solids. It is based on the development of an algorithm for creating both on intergranular surfaces and in the volume of particles nanosized inclusions, crystallites, structural defects. Taking into account the accumulated results of systematic studies of simple, binary systems as previous experience for further design of more complex systems, for correctly overcome the fundamental disadvantages, associated with the inconsistency of multicomponent systems, the sequence of physico-chemically substantiated technological stages on the way of formation of functional architecture has been formulated. The coevolutionary concept of self-organization of chemical systems is also formulated, according to which the regulation of the course of structural-functional reorganization processes takes place by two mechanisms: adaptation and bifurcation. Taking into account the physicochemical properties, optimal conditions for the formation of element oxide clusters and the peculiarities of interparticle interaction, the course of structural and functional self-organization – response of colloidal solutions of a multicomponent system to directionally initiated changes in the characteristics of the dispersed reaction medium and, accordingly, the parameters of particles that are deliberately designed in this way (size, shape, composition, structure of their ensembles), as well as the effect on interparticle distances, hierarchy of structural levels, the action of concentration and temperature factors and the introduction of a modifying reagent were diagnosed by various measurements. The driving forces (electronegativity, competitive rearrangements) and tendencies of energy-supplied bifurcation formation of coordination polyhedra of structure-forming ions in multicomponent ensembles were identified, namely, the pathways of directed initiated rearrangement of the atomic architecture with the organization of oxygen-unsaturated zirconium-containing sites, which determined the matrix formation with practically significant catalytic activity.","PeriodicalId":23394,"journal":{"name":"Ukrainian Chemistry Journal","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2022-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78123124","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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