Oleg V. Mikhailov

From novel complexing conditions to novel coordination compounds of nickel(II) with dithiooxamide and its bulky analogues

SummaryNovel complexing processes in the NiII-dithiooxamide, NiII-N,N′-diphenyldithiooxamide and NiII-quinoxaline-2,3-dithiol systems, which have not been used in coordination chemistry before, namely complexing in a nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix in contact with an aqueous solution of the corresponding ligand, have been studied. Under these specific conditions, in the NiII-dithiooxamide system, five different coordination compounds are formed, four of which are insoluble in H2O. In the NiII-quinoxaline-2,3-dithiol system, three different complexes formed (each of them insoluble in H2O) and, in the NiII-diphenyldithiooxamide system, only one insoluble complex is formed. Whereas, complexing in solution or the solid phase, formation of only one complex is observed in each of systems cited

Gelatin-immobilized metal complexes: synthesis and applications

Formation of p-, d- and f-metal complex gelatin-immobilized matrix systems using reactions of electrophilic, nucleophilic substitution and template synthesis, and employment of these materials in photographic processes, in spectroscopy and for absorption of metal ions, have been summarized and discussed. The review covers the period 1990–2005.

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 (pH ∼ 12) 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.

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.

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.

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

SummaryComplexing 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-SN1-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.ZusammenfassungEs 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-SN1-Mechanismus verläuft. Es werden die entsprechenden Reaktionsschemata angegeben. Beispiele für den kinetischen Verlauf für bestimmte „Hexacyanoferrat(II)-Cu(II)-Ligand“-Systeme werden präsentiert.

Soft template synthesis in copper(II)–dithiooxamide–methanal, copper(II)–dithiooxamide–ethanal and copper(II)–dithiooxamide–propanone triple systems in a copper(II)hexacyanoferrate(II) gelatin-immobilized matrix

Novel complexing processes in the CuII–dithiooxamide–methanal, CuII–dithiooxamide–ethanal and CuII–dithiooxamide–propanone triple systems proceeding under specific conditions, to copper(II)hexacyanoferrate(II) gelatin-immobilized matrix systems in contact with aqueous-alkaline (pH ∼ 12) solutions containing dithiooxamide and methanal, ethanal or propanone, have been studied. It has been shown that template synthesis leading to the formation of macrocyclic coordination compounds (2,8-dithio-3,7-diaza-5-oxanonandithioamide-1,9)copper(II), (2,8-dithio-3,7-diaza-4,6-dimethyl-5-oxanonandithio-amide-1,9)copper(II) and (4,4′,6-trimethyl-2,8-dithio-3,7-diazanonen-6-dithioamide-1,9)copper(II), respectively, takes place under such conditions. Dithiooxamide, methanal, ethanal and propanone act as ligand synthons in these processes.

On the possibility of template synthesis in the ternary system of vanadium(IV)-dithiooxamide-formaldehyde

With application of hybride method of density functional B3LYP with the 6–31G(d) basis set we calculated geometric parameters of macrocyclic complexes formed at the template reactions in the system V(IV)-dithiooxamide-formaldehyde of dioxovanadium(IV). The complexes are formed by tetradentate chelate ligands by means of (NNSS)- and (NNNN)-coordination of donor centers. Atomic coordinates and bond lengths of the formed complexes are listed. The values of enthalpy and Gibbs energy of the formation of the complexes are calculated and it is resumed that the template synthesis in such system can be realized at the complex formation in gelatin-immobilized matrix only.

Quantum-chemical calculation of steric structure of the complexes formed at template synthesis in three-component systems of Co(II) [Ni(II), Cu(II)] ion-bithiooxamide-acetone

By means of hybrid method of the density functional B3LYP with 6-31G(d) basis set we carried out calculation of geometric parameters of Co(II), Co(III), Ni(II) and Cu(II) complexes with macrocyclic ligand formed at the template processes in the systems M(II)-dithiooxamide-acetone with NNSS-coordination of donor centers. Atomic coordinates, bond lengths, bond angles and dihedral angles in the complexes with metallochelate node MN2S2 are listed. In the cases of Ni(II) and Cu(II) this chelate node is practically planar while in the case of Co(II) is tetrahedral. An additional six-membered metallocycle formed as a result of template “stitching” is screwed and turned by enough significant angle relative to five-membered rings.

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

SummaryComplexing 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 SN2-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.ZusammenfassungEs 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 SN2-Mechanismus verläuft. Es werden die entsprechenden Reaktionsschemata angegeben. Beispiele für den kinetischen Verlauf für bestimmte „Hexacyanoferrat(II)-Ni(II)-Ligand“-Systeme werden präsentiert.