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.     

Template synthesis in the nickel(II)–thiocarbohydrazide–propanone triple system

The complexing process proceeding in the Ni^II–thiocarbohydrazide (H₂N–H–NC(=S)–NH–NH₂)–propanone triple system in EtOH solution and nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix has been studied. It has been found that in the first case, template synthesis leading, as a minimum, to formation of three coordination compounds of Ni^II with (N,N,S,S)-donor tetradentate ligands having NiL¹, NiL² and NiL³compositions where L¹ is 4,6,6-trimethyl-2,3,7,8-tetraazanonen-3-di(thiohydrazide)-1,9, L² is 4,6,6,12-tetrametyl-1,9-dithio-2,3,7,8,10,11-hexaazatridekadien-3,11-hydrazide-1 and L³ is 2,8,10,10,16-pentamethyl-5,13-dithio-3,4,6,7,11,12,14,15-octaazaheptadekatrien-2,7,15 is observed, whereas in the gelatin-immobilized matrix, a complexing process in the system considered does not occur.     

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.     

Mild template synthesis of copper(II)-containing macrocyclic compounds in the CuII–1,2-diaminoethanedithione-1,2–ethanedione-1,2 and CuII–1,2-diamino-ethanedithione-1,2–butanedione-2,3 triple systems into Cu2[Fe(CN)6]-gelatin-immobilized matrix implantates

The complexing processes in the Cu^II–1,2-diaminoethanedithione-1,2–ethanedione-1,2 and Cu^II–1,2-diaminoethanedithione-1,2–butanedione-2,3 triple systems occuring in the copper(II)hexacyanoferrate(II) gelatin-immobilized matrix in contact with aqueous alkaline solutions (pH~12) containing 1,2-diaminoethanedithione-1,2 and ethanedione-1,2 or butanedione-1,2 under room temperature, and between MCl₂, 1,2-diaminoethanedithione-1,2 and ethanedione-1,2 or butanedione-1,2 in the ethanol solutions, upon heating up to ~80 °C, have been studied. In both systems indicated, template synthesis occurs in the gelatin-immobililized matrix but does not occur in the ethanol solution. As a result of template synthesis, macrocyclic Cu^II chelates with 2,7-dithio-3,6-diazaoctadien-3,5-dithioamide-1,8 and its 4,5-dimethylsubstituted derivative are formed in the gelatin-immobililized matrix. 1,2-diaminoethanedithione-1,2 and ethanedione-1,2 or butanedione-2,3 are the ligand synthons in the processes indicated.     

On template synthesis in the ternary system Ni(II)-thiosemicarbazide-diacetyl

A new complexation process in the ternary system Ni(II)-hydrazinomethanethioamide (thiosemicarbazide)-2,3-butanedione (diacetyl) has been studied. Complexation occurs in an aqueous ethanol solution and in nickel(II) hexacyanoferrate(II) gelatin-immobilized matrix systems. It has been shown that, under these conditions, the process involves the “self-assembly” (template synthesis) of Ni(II) macrotricyclic complexes with a new chelating ligand—4,5-dimethyl-1,8-dimercapto-2,3,6,7-tetraaza-1,3,5,7-octatet-raene-1,8-diamine with the (NSSN) coordination of donor atoms to the metal atom.     

Mild template synthesis of a macrocyclic Cu(II) chelate complex with 1,10-diamino-1,10-dimercapto-5,6-dimethyl-4,7-diazadeca-1,4,6,9-tetraene-3,8-dithione in Cu<Subscript>2</Subscript>[Fe(CN)<Subscript>6</Subscript>]-gelatin-immobilized matrix implantates

Complexation in Cu₂[Fe(CN)₆]-gelatin-immobilized matrix implantates in contact with alkaline (pH > 10) aqueous solutions containing propane-1,3-dithioamide and butane-2,3-dione, as well as with an ethanolic solution containing the same organic compounds, was studied. It was found that room-temperature complexation in the gelatin matrix gives a macrocyclic complex CuL¹with a tetradentate N,S,S,N-donor ligand via a template synthesis, while complexation in solution at room and higher temperatures yields only a bischelate Cu(II) complex with monodeprotonated propane-1,3-dithioamide. Schemes of the complexation processes were proposed. It was demonstrated that when propane-1,3-dithioamide and butane-2,3-dione are in direct contact in solution, the above N,S,S,N-donor ligand was formed in neither the presence nor the absence of Cu²⁺.     

Soft template synthesis in the cobalt(III)–1,2-diaminoethane-1,2-dithione–propanone triple system on a K[CoFe(CN)<Subscript>6</Subscript>]-gelatin-immobilized matrix

Complexation of Co^III, in the form of K[CoFe(CN)₆]-gelatin-immobilized matrix, in contact with aqueous-alkaline solutions (pH ∼ 12) containing 1,2-diaminoethane-1,2-dithione and propanone, has been studied. Template synthesis leading to a chelate Co^III coordination compound with a tetradentate N,N,S,S-donor ligand identified as 4,4,6-trimethyl-1,9-diamino-1,9-dimercapto-3,7-diazanon-3-en-2,8-dithione and hydroxy co-ligand occurs under these specific conditions. 1,2-Diaminoethane-1,2-dithione and propanone are the ligand synthons in this process.     

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 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.     

Template synthesis in the M(II)–thiocarbohydrazide–diacetyl triple system

Novel complexing processes in the Cu^II-thiocarbohydrazide-diacetyl triple system proceeding to a copper(II)hexacyanoferrate gelatin-immobilized matrix system in contact with aqueous-alkaline (pH 12) solutions containing thiocarbohydrazide and diacetyl, have been studied. It has been shown that mild template synthesis of copper(II) coordination compounds with (N,S,N,S)- and (N,N,N,N)- tetradentate ligands - 4,5-dimethyl-2,3,6,7-tetraazaoctadien-3,5-dithiohydrazide-1,8 and 3,10-dithio--6,7,13,14-tetramethyl-1,2,4,5,8,9,11,12-octaazacyclotetradecatetraene-1,5,7,12 take place, respectively. At the same time, the complexing process in the system under examination, when it occurs in aqueous-ethanol solution between CuCl₂ and the organic compounds indicated, leads to copper(II) coordination compounds with another (N,S,N,S)-tetradentate ligand - 3,9,10,16-tetramethyl-6,13--dimercapto-2,17-dioxo-4,5,7,8,11,12,14,15-tetraazaoctadecahexaene - 3,6,8,10,12,15. In both cases, thiocarbohydrazide and diacetyl are ligand synthons in these complexing processes.