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

Abstract

The complexing processes in the M II -dithiomalonamide-diacetyl triple system (M ¼ 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 MCl 2 , 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.

Molecular nanotechnologies of gelatin-immobilization using macrocyclic metal chelates

“…Recently, the ‘soft’ template synthesis in the Cu(II)–dithiomalonamide–diacetyl ( 87 , 88 ) and Cu(II)–thiocarbohydrazide–diacetyl ( 89 ) systems was observed. According to the published data, in the first of these systems, the process ( 4 .5) with the formation of the macrotricyclic complexes of the ( 656 ) type with the (NSSN) donor tetradentate chelant, 5,6-dimethyl-1,10-diamine-1,10-dimercapto-4,7-diazadecatetraen-1,4,6,9-dithione-3,8 [M L13] (M=Ni, Cu) takes place…”

Molecular and Electronic Structures of Macrocyclic Compounds Formed at Template Synthesis in the M(II)—Thiocarbohydrazide—Diacetyl Triple Systems: A Quantum-Chemical Analysis by DFT Methods

“…Previously, in [1], the template synthesis in the system Cu(II)-thiocarbohydrazide H 2 N-HN-C(=S)-NH-NH 2 -diacetyl Me-C(=O)-C(=O)-Me in copper(II)hexacyanoferrate (II) gelatin-immobilized matrix implants and the formation of a macrotetracyclic chelate of the indicated metal ion were described, in which the ligand contained in it, namely, the double-deprotonated form 3,10-dithio-6,7,13,14-tetramethyl-1,2,4,5,8,9,11,12-octaazacyclotetradecatetraene-1,5,7,12 (L 2− ), coordinated to Cu(II) via four donor nitrogen atoms (Figure 1). The question of the specificity of the molecular structure of this complex (CuL), however, has not yet been resolved, because neither in [1] nor any other researchers have been able to obtain single crystals of this compound suitable for XRD analysis. The complexes considered in the article [1] belong to the category of metal-macrocyclic compounds with a closed loop, in which the complex metal ion is located in the internal cavity of the macrocyclic organic compound.…”

“…The question of the specificity of the molecular structure of this complex (CuL), however, has not yet been resolved, because neither in [1] nor any other researchers have been able to obtain single crystals of this compound suitable for XRD analysis. The complexes considered in the article [1] belong to the category of metal-macrocyclic compounds with a closed loop, in which the complex metal ion is located in the internal cavity of the macrocyclic organic compound. Such complexes have a number of unique properties that are not inherent in the complexes of the same metals with acyclic ligands and, for this reason alone, are of considerable interest to modern fundamental chemistry.…”

“…In this context, it seems interesting and important to obtain objective data on the structural and geometric parameters of this chemical compound using quantum-chemical calculations using some version of the density functional theory (DFT), which is currently the most popular method for calculating the molecular and electronic structures of 3d-element complexes. On the other hand, it is very likely that in a similar way, i.e., as a result of the combination of the above ligand synthons, accompanied by intramolecular dehydration (Figure 2), the same complexes of chemical elements adjacent to copper, nickel, and zinc can be formed, although there is no information about this possibility either in [1] or in any other publications devoted to template synthesis. Since it is these two 3d elements that, in terms of the complexes they form, are closest to Cu(II) complexes compared to those for the other d-elements, it seems appropriate, first, to confirm the possibility of the existence of Ni(II) and Zn(II) metal chelates with the above ligand L 2− , and secondly, in case of a positive answer to this question, compare the parameters of their molecular and electronic structures, as well as their thermodynamic characteristics, with similar parameters for the CuL complex.…”

Synthesis and Characterization of New Schiff Bases Derived from N (1)‐Substituted Isatin with Dithiooxamide and Their Co(II), Ni(II), Cu(II), Pd(II), and Pt(IV) Complexes

“…The present work aims to study the synthesis and antibacterial activity of three new ligands derived from condensation of N-acetyl, N-benzyl, and N-benzoylisatin with the chelating agent dithiooxamide (ethanedithioamide or rubeanic acid) dto and their metal complexes. The Schiff bases of dithiooxamide and their complexes have received most of the attention because of the semiconductive, magnetic, spectroscopic, and thermal properties [ 15 – 17 ] as well as being used as semiconductors antibacterial and antifungal agents [ 18 – 20 ].…”