Complexing of nickel(II) with 8-mercaptoquinoline and of its 5-derivatives in nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix systems

Complexing processes in systems containing NiII and 8-mercaptoquinoline or its derivatives (5-chloro-, 5-bromo-, 5-phenyl, 5-thiomethyl-8-mercaptoquinoline and 5,8-dimercaptoquinoline) take place in the nick- el(II)hexacyanoferrate(II) gelatin-immobilized matrix (GIM) in contact with an aqueous solution of the corresponding ligand. Under the conditions specified, in the NiII-8-mercaptoquinoline, NiII-5-chloro-8-mer captoquinoline,NiII-5-bromo-8-mercaptoquinoline, NiII-5-phenyl-8-mercaptoquinoline and NiII-5-thiomethyl-8-mercaptoquinoline systems, one water-insoluble complex of NiB2 composition (B– is a singly deprotonated ligand) is formed. In the NiII-5,8-dimercaptoquinoline system, two insoluble complexes, monomeric Ni(HB)2 and polymeric [Ni2B2(H2O)2]n (HB– is the singly, and B2– the doubly deprotonated form of the ligands) are generated. Upon complexing in solution or the solid phase, the formation of only one complex is observed in each of systems cited.     

Complexing processes in M(II)-dithiomalonamide-diacetyl triple systems (M= Ni,Cu) in ethanol solution and in a metal(II)hexacyanoferrate(II) gelatin-immobilized matrix materials

The complexing processes in the M ^II -dithiomalonamide-diacetyl triple system (M=Ni, Cu) occuring in the nickel(II)- and copper(II)hexacyanoferrate(II) gelatin-immobilized matrix in contact with aqueous alkaline solutions (pH~12) containing dithiomalonamide and diacetyl at room temperature, and between MCl₂, dithiomalonamide and diacetyl in EtOH solutions upon heating to$80°C, have been studied. In the Ni ^II -dithiomalonamide-diacetyl system, template synthesis occurs in EtOH solution but does not occur in the gelatin-immobilized matrix, whereas in the Cu ^II -dithiomalonamide-diacetyl system, template synthesis occurs in the gelatin-immobilized matrix but not in EtOH solution. Dithiomalonamide and diacetyl are the ligand synthons in the processes indicated.     

Cobalt(III)-8-mercaptoquinoline complexing in cobalt(III)hexacyanoferrate(II) gelatin-immobilized matrix systems

Novel complexing processes in binary systems containing Co^III and 8-mercaptoquinoline or its derivatives (5-Cl-, 5-Br-, 5-Me-, 5-Ph- and 5-SMe- 8-mercaptoquinoline), with a cobalt(III)hexacyanoferrate(II) gelatin-immobilized matrix in contact with an aqueous solution of the corresponding ligand, have been observed. Under the specific conditions described, three water-insoluble coordination compounds are formed in each of the systems indicated, whereas upon complexing in solution or the solid phase the formation of only one complex is observed.     

Cobalt(II)-8-mercaptoquinolines complexing in cobalt(II) hexacyanoferrate(II) gelatin-immobilized matrix materials

Complexing processes between Co^II and 8-mercaptoquinoline, or its various alkyl- and aryl-substituted derivatives, in contact with Co₂[Fe(CN)₆]-gelatin-immobilized matrix materials, with aqueous solutions of corresponding ligands, have been studied. When R² = Me or Ph, formation of Co^II chelates having a 1:2 metal ion/singly deprotonated ligand is observed, whereas when R² = H, formation of Co^III chelates having metal ion/singly deprotonated ligand 1:3 ratios occur.     

Mild template synthesis in the CoII-dithiooxamide-glyoxal system in cobalt(II) hexacyanoferrate(II) gelatin-immobilized matrices

Complexation processes in a cobalt(II) hexacyanoferrate(II) gelatin-immobilized matrix under the action of aqueous solutions containing dithiooxamide H₂N−C(S)−C(S)−NH₂ and glyoxal HOC−CHO at pH>10 were studied. Under these conditions, mild template synthesis occurs to form a Co^III chelate with the (N,N,S,S)-ligand,viz. 2,7-dithio-3,6-diazaoctadiene-3,5-dithioamide-1,8, with a metal to ligand ratio of 1∶1, where dithiooxamide and glyoxal act as ligand synthons. The reaction mechanism is discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1999–2004, October, 1999.     

Complexing processes on the immobilized matrices of hexacyanoferrate(II) copper(II) and nitrogen-sulfur-containing ligands in thin gelatin layer

Summary Complexing processes occurring between immobilized matrices obtained from Cu(II) hexacyanoferrates(II) and solutions of various nitrogen-sulfur-containing chelating ligands in thin gelatin layers have been studied. With Cu₂[Fe(CN)₆]-matrix, the complexing process is found to proceed according to pseudo-S_N1-mechanism. The schemes of the processes in each of the above matrices are given. Examples of kinetic curves for particular systems hexacyanoferrate(II)copper(II)-ligand are presented.

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Komplexierungsprozesse auf den immobilen Matrices von Hexacyanoferrat(II)-Kupfer(II) und N-Shaltigen Liganden in dünnen Gelatin-Schichten

Zusammenfassung Es wurden Komplexierungsprozesse auf immobilisierten Matrices, die von Cu(II)-Hexacyanoferrat(II) und Lösungen verschiedener Stickstoff-Schwefel-Liganden erhalten wurden, in dünnen Gelatin-Schichten untersucht. Mit einer Cu₂[Fe(CN)₆]-Matrix wurde festgestellt, daß der Komplexierungsprozeß nach einem Pseudo-S_N1-Mechanismus verläuft. Es werden die entsprechenden Reaktionsschemata angegeben. Beispiele für den kinetischen Verlauf für bestimmte Hexacyanoferrat(II)-Cu(II)-Ligand-Systeme werden präsentiert.

     

Novel coordination compounds of nickel(II) and copper(II) with N,Nprime-diphenylthiooxamide; formation of complexed metalhexacyanoferrate(II) gelatin-immobilized matrix systems

A novel route to complexes of NiII and CuII with N,Nprime-diphenylthiooxamide, namely complexing in a NiII or CuII hexacyanoferrate(II) gelatin-immobilized matrix in contact with an aqueous solution of the N,Nprime-diphenylthiooxamide, has been studied. Under these specific conditions, in the NiII system, four different coordination compounds are formed, three of which are insoluble in H2O; in the CuII system, only one insoluble complex is formed. When complexation is carried out in solution or the solid phase, formation of only one complex is observed in each of systems studied. This revised version was published online in June 2006 with corrections to the Cover Date.     

Iron(II)-8-mercaptoquinoline,iron(II)-5-chloro-8-mercaptoquino-line and iron(II)-5-bromo-8-mercaptoquinoline complexing in the iron(III) hexacyanoferrate(II) gelatin-immobilized matrix systems

Novel complexing processes in the Fe^II-8-mercaptoquinoline, Fe^II-5-chloro-8-mercaptoquinoline and Fe^II-5-bromo-8-mercaptoquinoline systems, not used previously in coordination chemistry, namely complexing as an iron(III)hexacyanoferrate(II) gelatin-immobilized matrix (GIM) in contact with an aqueous solution of the corresponding ligand, have been observed and analysed. Incorporation of these ligands into the inner coordination sphere is preceded by the decomposition of the immobilized compound KFe[Fe(CN)₆] to form hydroxides or oxohydroxides of Fe^II and Fe^III under the action of OH^- ions. It has been shown that Fe^IIFeIII redox process and the formation of FeB₃ chelates (B^- is a singly deprotonated form of the corresponding ligand) take place during complexing under such conditions.     

Tuning the thermal stability of copper(II) hexacyanoferrate(II) nanoparticles

Journal of Thermal Analysis and Calorimetry - It is well known that the physical properties of nanoparticles can be tuned by controlling synthetic factors such as pH, temperature, reactant ratio or...     

New inclusion compound — copper(II) hexacyanoferrate in faujasite

The copper(II) hexacyanoferrate lattice is formed within the zeolite when CuSO₄ reacts with hexacyanoferrate (II) encapsulated in faujasite under hydrothermal conditions. A quantity, of Cu²⁺ in excess of that necessary for ion exchange has an important role in forming the three dimensional structure, apparently through interactions with the zeolite skeleton. Formation of the hexacyanoferrate is accompanied by considerable deformation of the faujasite skeleton.L. V. Pisarzhevskii Institute of Physical Chemistry, Ukraine National Academy of Science, Ukraine, 252039 Kiev, Nauki Prospekt 31. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 32, No. 1, pp. 43–46, January–February, 1996. Original article submitted April 27, 1995.     

Soft template synthesis of (2,8-dithio-3,7-diaza-5-oxanonandithioamide-1,9) nickel(II) and (2,7-dithio-3,6-diazaoctadien-3,5-dithioamide-1,8)nickel(II) using a nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix

Complexing processes leading under specific conditions to nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix systems in contact with aqueous-alkaline solutions (pH12) containing dithiooxamide and formaldehyde or glyoxal, have been studied. It has been shown that template synthesis of macrocyclic co-ordination compounds, (2,8-dithio-3,7-diaza-5-oxanonandithioamide-1,9)nickel(II) and (2,7-dithio-3,6-diazaoctadien-3,5-dithioamide-1,8)nickel(II), occurs. Dithiooxamide, formaldehyde and glyoxal act as ligand synthons in this process.     

Complexing processes on the immobilized matrices of hexacyanoferrate(II)-nickel(II) and nitrogen-sulfur ligands in thin gelatin layer

Summary Complexing processes occurring between immobilized matrices obtained from Ni(II) hexacyanoferrates(II) and solutions of various nitrogen-sulfur-containing chelating ligands in thin gelatin layers have been studied. With Ni₂[Fe(CN)₆]-matrix, the complexing process is found to proceed according to a S _N ² -mechanism. The schemes of the processes in each of the above matrices are given. Examples of kinetic curves for particular systems hexacyanoferrate(II) nickel(II)-ligand are presented.

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Komplexierungsprozesse auf den immobilisierten Matrices von Hexacyanoferrat(II)-Nickel(II) und Stickstoff-Schwefel-Liganden in dünnen Gelatin-Schichten

Zusammenfassung Es wurden Komplexierungsprozesse auf immobilisierten Matrices, die von Ni(II)-Hexacyanoferrat(II) und Lösungen verschiedener Stickstoff-Schwefel-Liganden erhalten wurden, in dünnen Gelatin-Schichten untersucht. Mit einer Ni₂[Fe(CN)₆]-Matrix wurde festgestellt, daß der Komplexierungsprozeß nach einem S _N ² -Mechanismus verläuft. Es werden die entsprechenden Reaktionsschemata angegeben. Beispiele für den kinetischen Verlauf für bestimmte Hexacyanoferrat(II)-Ni(II)-Ligand-Systeme werden präsentiert.

     

Self-assembly of supramolecular Ni(II) and Cu(II) metalmacrocyclic compounds with tetraazamacrocyclic ligand into a gelatin-immobilized matrix

Self-assembly in M(II)-ethanedithioamide [H₂N–C(=S)–C(=S)–NH₂]-propanone triple systems (M=Ni, Cu) into corresponding metal(II) hexacyanoferrate(II) gelatin-immobilized matrix systems under contact with aqueous-alkaline (pH?～?12) solutions containing ethanedithioamide and propanone have been studied. Formation of supramolecular macrotetracyclic compounds of Ni(II) and Cu(II) with 2,7,7,9,14,14-hexamethyl-3,6,10,13-tetraazacyclotetradecadien-2,9-tetrathione-4,5,11,12 containing original “kernel” (metal complex) and “shell” surrounding this “kernel”, of polypeptide chains of the gelatin molecules, occurs under such specific conditions.     

Kinetics and mechanism of thermal decomposition of cadmium(II) complexes with substituted thioureas

From the thermal decomposition curves of cadmium(II) complexes with substituted thioureas (methyl-, dimethyl-, ethyl-, diethyl-, butyl-, dibutyl-, phenyl-, diphenyl-, acetyl- and benzoylphenylthiourea), the kinetic parameters of the thermal decompositions of these complexes were determined and a decomposition mechanism was suggested. The following thermal stability sequence is given for the Cd(II) complexes: complexes with alkylthioureas < complexes with phenylthioureas < complexes with acylthioureas.

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Zusammenfassung Die kinetischen Parameter der thermischen Zersetzung von Verbindungen der Formeln Cd(MeTM)₄(ClO₄)₂, Cd(DMeTM)₄(ClO₄)₂, Cd(EtTM)₄(ClO₄)₂, Cd(DEtTM)₄(ClO₄)₂, Cd(BuTM)₄(CtO₄)₂, Cd(DBuTM)₄(ClO₄)₂, Cd(AcTM)₃(ClO₄)₄, Cd(FTM)₄(ClO₄)₂ und Cd(DFTM)₄(ClO₄)₂ wurden mittels TG and DTG untersucht. Die Reaktionsordnung (n) und die Aktivierungsenergie (E _a) wurden nach der graphischen Methode ermittelt.

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Soft template synthesis of cobalt(III) chelates with 2,8-dithio-3, 7-diaza-5-oxa-nonandithioamide-1,9 and with 2,7-dithio-3,6-diazaoctadien-3, 5-dithioamide-1,8 into cobalt(III)hexacyanoferrate(II) gelatin-immobilized matrix materials

The complexing processes in the triple Co^III–dithiooxamide–methanal and Co^III–dithiooxamide–glyoxal systems taking place in the KCoFe(CN)₆-gelatin-immobilized matrix in contact with aqueous-alkaline solutions (pH~12) containing (dithiooxamide + methanal) and (dithiooxamide + glyoxal), have been studied. Template synthesis leading to macrocyclic Co^III coordination compounds with tetradentate N,N,S,S-donor ligands-(2,8-dithio-3,7-diaza-5-oxanonandithioamide-1,9) and (2,7-dithio-3,6-diazaoctadien-3,5-dithioamide-1,8) occurs under these specific conditions. Dithiooxamide, methanal and glyoxal are the ligand synthons in these processes.     

Mild template synthesis of a copper(II)-containing macrocyclic compound with 4,4,6-trimethyl-2,3,7,8-tetraazanonen-6-dithiohydrazide-1,9 in a gelatin-immobilized matrix

The complexing processes in the triple copper(II)–thiocarbohydrazide–propanone system taking place in a copper(II) hexacyanoferrate(II) gelatin-immobilized matrix in contact with aqueous-alkaline solutions (pH12), containing thiocarbohydrazide and propanone, have been studied. Template synthesis leading to a macrocyclic coordination compound with the tetradentate N,N,S,S-donor ligand, (4,4,6-trimethyl-2,3,7,8-tetraazanonen-6-dithiohydrazide-1,9), occurs under these specific conditions when thiocarbohydrazide and propanone are the ligand synthons.     

相转移催化法合成双3－苯丙烯酰基取代硫脲及双3－苯丙烯酰基取代胺衍生物

以3－苯丙烯酸为原料，经酰氯化，得到3－苯丙烯酰氯，在PEG－400为催化剂 的固液相转移催化条件下与硫氰酸铵及二胺类反应，一锅法制得双3－苯丙烯酰基 取代硫脲化合物。3－苯丙烯酰氯在PEG－600为催化剂的液液相转移催化条件下和 二胺类反应得到双－苯丙烯酰基取代胺化合物。反应条件温和、产率高。化合物经 元素分析、IR及^1H NMR证实。初步的生理活性研究表明，部分化合物具有良好的 抗炎活性。     

Thermal decomposition of hydrotalcitewith hexacyanoferrate(II) and hexacyanoferrate(III) anions in the interlayer

The thermal decompositions of hydrotalcites with hexacyanoferrate(II) and hexacyanoferrate(III) in the interlayer have been studied using thermogravimetry combined with mass spectrometry. X-ray diffraction shows the hydrotalcites have a d(003) spacing of 11.1 and 10.9 Å which compares with a d-spacing of 7.9 and 7.98 Å for the hydrotalcite with carbonate or sulphate in the interlayer. XRD was also used to determine the products of the thermal decomposition. For the hydrotalcite decomposition the products were MgO, Fe₂O₃ and a spinel MgAl₂O₄. Dehydration and dehydroxylation take place in three steps each and the loss of cyanide ions in two steps.     

Decomposition of hexacyanoferrate(II) in analysis

Summary On the base of the catalytic effect of Ag⁺ upon the decomposition of [Fe(CN)₆]^4–, a very sensitive spot test for the detection of silver has been developed. The sensitivity of the test for the pure system is 0,00075 g/ drop at the concentration limit 146.400.000. Hg, Au and Pd react analogously. Chlorides and bromides even in high concentrations do not impair the detection of silver. In presence of iodides the sensitivity of the test is slightly reduced.

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Zusammenfassung Es wurde eine sehr empfindliche Tüpfelprobe zum Nachweis von Silber entwickelt. Sie beruht auf der katalytischen Zersetzung des [Fe(CN)₆]^4–-Komplexes durch Silberionen. In reinen Lösungen können noch 0,00075 g Silber in einem Tropfen nachgewiesen werden (Grenzkonzentration: 146400000). Hg, Au und Pd reagieren ähnlich wie Ag. Chlorid und Bromid stören auch in großen Mengen nicht. Jodid setzt die Empfindlichkeit des Nachweises etwas herab.

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Part V.: Acta Pharm. Jug., 10, 37 (1960).     

Thermal decomposition of hydrotalcite with hexacyanoferrate(II) and hexacyanoferrate(III) anions in the interlayer

The mechanism for the decomposition of hydrotalcite remains unsolved. Controlled rate thermal analysis enables this decomposition pathway to be explored. The thermal decomposition of hydrotalcites with hexacyanoferrate(II) and hexacyanoferrate(III) in the interlayer has been studied using controlled rate thermal analysis technology. X-ray diffraction shows the hydrotalcites have a d(003) spacing of 10.9 and 11.1 Å which compares with a d-spacing of 7.9 and 7.98 Å for the hydrotalcite with carbonate or sulphate in the interlayer. Calculations show dehydration with a total loss of 7 moles of water proving the formula of hexacyanoferrate(II) intercalated hydrotalcite is Mg₆Al₂(OH)₁₆[Fe(CN)₆]_0.5·7H₂O and 9.0 moles for the hexacyanoferrate(III) intercalated hydrotalcite with the formula of Mg₆Al₂(OH)₁₆[Fe(CN)₆]_0.66·9H₂O. CRTA technology indicates the partial collapse of the dehydrated mineral. Dehydroxylation combined with CN unit loss occurs in two isothermal stages at 377 and 390°C for the hexacyanoferrate(III) and in a single isothermal process at 374°C for the hexacyanoferrate(III) hydrotalcite.