Marina A. Kazymova

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 (pH∼12), 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.

Soft template synthesis of macrocyclic copper(II) chelates with 3,9-dithio-4,8-diaza-6-oxaundekandithioamide-1,11 in a Cu2[Fe(CN)6]-gelatin-immobilized matrix

The complexing processes in the triple copper(II)–dithiomalonamide–methanal system taking place in the copper(II)hexacyanoferrate(II)-gelatin-immobilized matrix in contact with aqueous alkaline solutions (pH∼12), containing dithiomalonamide and methanal, have been studied. Template synthesis leading to a macrocyclic coordination compound with the tetradentate N,N,S,S-donor ligand, (3,9-dithio-4,8-diaza-6-oxaundekandithioamide-1,11), occurs under these specific conditions when dithiomalonamide and methanal are the ligand synthons.

Copper(II)- Heterocyclic Compounds with 4,5-Dimethyl-2,3,6,7- tetraazaoctadien-3,5-dithiohydrazide-l,8 and 3,10-Dithio-6,7,13,14- tetramethyl-l,2/4,5,8/9/ll,12-octaazacyclotetradekatetraen-l,5,7,12 Obtained in Gelatin- Immobilized Matrix as a Result of Template Synthesis

Soft template synthesis of macrocyclic coordination compounds with 4,5-dimethyl-2,3,6,7tetraaza-octadien-3,5-dithiohydrazide-l,8 and 3,10-dithio-6,7,13,14-tetramethyl1,2,4,5,8,9,11,12-octaazacyclo-tetradekatetraen-l, 5,7,12 in the triple Cu(ll)thiocarbohydrazide2,3butanedione system in the copper(ll)hexacyanoferrate(ll) gelatinimmobilized matrix has been carried out. Also, it has been established that similar process in the nickel(ll)hexacyanoferrate(ll) matrices does not occur under such conditions.

Cobalt(III)-dithiooxamide, cobalt(III)-N,N′-diphenylthiooxamide and cobalt(III)-N,N′-diphenyldithiooxamide complexing in the KCo[Fe(CN)6]-gelatin-immobilized matrices

Novel complexing processes by CoIII-dithiooxamide, CoIII-N,N′-diphenylthiooxamide and CoIII-N,N′-diphenyldithiooxamide systems, with a cobalt(III)hexacyanoferrate(II) gelatin-immobilized matrix in contact with an aqueous solution of the corresponding ligand, have been observed and analyzed. Under the specific conditions described, four different coordination compounds are formed in the CoIII-dithiooxamide system, three of which are insoluble in water, whereas in each of the CoIII-N,N′-diphenylthiooxamide and CoIII-N,N′-diphenylthiooxamide systems, three water-insoluble coordination compounds are formed. In solution or the solid phase, formation of only one complex is observed, in each of the systems studied.

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.

Complexing reactions in the Ni(II)-5-methyl-4-amino-3-thiooxo-1,2,4-triazapentene-1-methanal and Ni(II)-5-methyl-4-amino- 3-thiooxo-1,2,4-triazapentene-1-propanone triple systems

Complexing processes in the NiII-TTA-methanal (A) and NiII-TTA-propanone (B) triple systems (TTA–5-methyl-4-amino-3-thiooxo-1, 2, 4-triazapentene-1) in ethanol solution and nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix have been studied. In the NiII-TTA- methanal system, formation of NiII oligomeric coordination compounds in which metal chelate cycles are connected by–H2C–O–CH2–structural groups, takes place. In the NiII-TTA-propanone triple system, formation of only NiII complexes with TTA takes place. No complexing process in the triple systems in nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix was found.

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.

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 FeII-8-mercaptoquinoline, FeII-5-chloro-8-mercaptoquinoline and FeII-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 FeII and FeIII under the action of OH- ions. It has been shown that FeII→FeIII 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.