O. V. Mikhailov

Calculation of geometric parameters and energies of macrocyclic metal chelates in the ternary M(II) ion-thiocarbamoylmethanamide-formaldehyde systems

The thermodynamic and geometric parameters of isomeric macrotricyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes that can, in principle, be the products of the reaction of corresponding hexacyanoferrates(II) with thiocarbamoylmethanamide H2N-C(=S)-C(=O)-NH2 and formaldehyde in gelatin-immobilized matrix implants have been calculated by the hybrid B3LYP density functional theory method with the use of the 6–31G(d) basis set and the Gaussian 98 program package. For any of the M(II) ions under consideration, the most stable complexes have the MN4 metal chelate cores. The bond lengths and bond angles in these complexes have been reported, and it has been stated that the five-membered chelate rings in the complexes are not strictly planar. The additional six-membered chelate ring resulting from template cross-linking is also nonplanar and, in some cases, is turned at a rather large angle to the five-membered rings.

Calculation of geometric parameters of macrocyclic metal chelates formed by template synthesis in tertiary systems M(II) ion-ethanedithioamide-formaldehyde-ammonia

The geometric parameters of macrotricyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with 2,8-dithio-3,5,7-triazanonanedithioamide-1,9 with the (N,N,S,S) coordination of the chelant donor centers (formed by template synthesis in the M(II)-ethanedithioamide-formaldehyde-ammonia system) have been calculated by the hybrid B3LYP density functional theory method with the use of the 6-31G(d) basis set and the Gaussian 98 program package. The bond lengths and bond angles in the complexes with the MN2S2 coordination core have been reported. Calculations demonstrated that in none of the complexes are the five-membered chelate rings planar and that these rings in the Zn(II) complex are significantly different. For all M(II) ions under consideration, an additional six-membered chelate ring resulting from template cross-linking is turned at a rather large angle to the two five-membered rings and this ring itself is nonplanar.

Geometric parameters and energies of molecular structures of macrocyclic metal chelates in the ternary 3d M(II) ion-ethanedithioamide-ethanedial systems according to quantum-chemical DFT B3LYP calculations

The thermodynamic and geometric parameters of isomeric macrotricyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the (NSSN) coordination of the ligand donor centers formed in the reaction of corresponding hexacyanoferrates(II) with ethanedithioamide H2N-C(=S)-C(=S)-NH2 and ethanedial HC(=O)-CH(=O) in gelatin-immobilized matrix implants have been calculated by the hybrid B3LYP density functional theory method with the use of the 6–31G(d) basis set and the Gaussian 03 program package. The bond lengths and bond and torsion angles in these complexes have been reported, and it has been stated that the Mn(II), Co(II), and Cu(II) complexes are nearly planar, the Fe(II) and Ni(II) complexes are slightly nonplanar, while the Zn(II) complex exhibits a rather considerable deviation from coplanarity. The additional five-membered chelate ring resulting from template cross-linking is almost planar in all cases.

Density functional theory calculation of molecular structures of (5656)macrotetracyclic 3d metal complexes with 4,12-Dithiooxo-1,8-dioxa-3,6,10,13-tetraazacyclotetradecanedione-5,11

The geometric parameters of macrotetracyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the (NNNN) coordination formed by the reaction of corresponding hexacyanoferrates(II) with thiocarbamoylmethanamide H2N-C(=S)-C(=O)-NH2 and formaldehyde in gelatin-immobilized matrices have been calculated by the hybrid B3LYP density functional theory method with the use of the 6-31G(d) basis set and the Gaussian 03 program package. The bond lengths and bond and torsion angles in these complexes have been reported. It has been stated that the additional six-membered chelate rings resulting from template cross-linking are nonplanar and are turned at rather large angles to the two five-membered rings (which are also noncoplanar). In the Fe(II), Co(II), and Ni(II) complexes, the O1 and O2 atoms and both six-membered rings are located on one side of the (NNNN) plane of the donor nitrogen atoms, whereas in the Mn(II), Cu(II), and Zn(II) complexes, they are located on both sides of this plane.

Molecular structure and thermodynamic parameters of (5656)macrotetracyclic chelates in the 3d-element(ii) ion-hydrazinomethanethiohydrazide-2,3-butanedione ternary system according to density functional quantum-chemical calculations

The thermodynamic and geometric parameters of the macrocyclic chelates of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) with the (NNNN) coordination of the ligand donor centers formed upon complexation between the above metal ions, hydrazinomethanethiohydrazide (H2N-HN-C(=S)-NH-NH2), and 2,3-butanedione (H3C-C(=O)-C(=O)-CH3) in gelatin-immobilized matrix implants were calculated by the B3LYP 6–31G(d) density functional theory method with the use of the Gaussian 09 program package. The bond lengths, valence angles, and torsion angles were reported, and it was noted that the complexes of Fe(II), Co(II), Ni(II), and Cu(II) are almost planar, whereas the complexes of Mn(II) and Zn(II) have a quasi-pyramidal structure of the chelate unit. The additional six-membered metallocycles resulting from template cross-linking, as well as five-membered rings, are almost planar.

Quantum-chemical calculation of molecular structures of (5656)macrotetracyclic 3d-metal complexes “self-assembled” in quaternary systems M(II) ion-ethanedithioamide-formaldehyde-ammonia by the density functional theory method

The geometric parameters of (5656)macrotetracyclic complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) with the NNNN-coordination of donor sites of the chelant formed by the template reactions in the M(II)-ethanedithioamide-formaldehyde-ammonia systems have been calculated by the OPBE/TZVP hybrid density functional theory (DFT) method with the use of the Gaussian09 program package. In all complexes, five-membered chelate rings (almost identical to each other in each complex) are nonplanar. For all M(II) ions under consideration, two additional six-membered nonplanar chelate rings formed as a result of template “cross-link” are turned at considerable angles with respect to the five-membered rings. The six-membered rings are located on different sides of the NNNN plane of the nitrogen donor atoms.

Molecular structures of “template” (5555)macrotetracyclic chelates of 3d M(II) ions with 1,4,7,10-tetraaza-1,3,8-dodecatriene-5,6,11,12-tetrathione according to DFT quantum-chemical calculations

The geometric parameters of the molecular structures of M(II) (5555)macrotetracyclic complexes with a tetradentate (NNNN) macrocyclic ligand, formed by template reactions in the systems M(II)-ethanedithioamide-ethanedial-1,2-ethenediol systems, as well as of the molecular structure of the template ligand forming the coordination sphere of these complexes, have been calculated by the OPBE/TZVP density functional theory method. The bond lengths and bond and torsion angles in the complexes, as well as the standard enthalpies, entropies, and Gibbs energies for each of them, are reported.

Molecular structures of (5656)macrotetracyclic 3d metal chelates formed in the M(II) ion–ethanedithioamide–formaldehyde systems according to the density functional theory method

The thermodynamic and geometric parameters of macrotetracyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the (NNNN)-coordination of donor sites of the ligand formed upon complexation of the corresponding metal(II) hexacyanoferrates(II) with ethanedithioamide (NH2-C(=S)–C(=S)–NH2) and formaldehyde (H2C(=O)) in gelatin-immobilized matrices, as well as of the 14-membered macrocyclic ligand (chelant) forming these complexes, have been calculated by the OPBE/TZVP density functional theory (DFT) method with the use of the Gaussian 09 program package. The fiveand sixmembered chelate rings formed as a result of template “cross-link” are nonplanar. For the six-membered rings, the deviation from coplanarity is significantly more pronounced. In all complexes, the O1 and O2 oxygen atoms and both six-membered rings are located on different sides of the NNNN plane of the nitrogen donor atoms.

Specifics of the molecular structures of “template” (5456)macrotetracyclic chelates of 3d M(II) Ions with 5,7,9-triimino-1-oxa-3,6,8,11-tetraazacyclododecane-4,10-dithione according to DFT calculations

The geometric parameters of the molecular structures of M(II) (5456)macrotetracyclic complexes with a tetradentate (NNNN) macrocyclic ligand, formed by template reactions in the quaternary systems M(II)-2-amino-2-thioxoacetamide (H2N-C(=S)-C(=O)-NH2)-aminomethanamidine (H2N-C(=NH)-NH2)-methanal (formaldehyde, CH2O) (M = Mn, Fe, Co, Ni, Cu, and Zn), as well as of the molecular structure of the template ligand per se, have been calculated by the OPBE/TZVP density functional theory method. The bond lengths and bond and torsion angles in these complexes have been reported. The standard enthalpies, entropies, and Gibbs energies of formation of these compounds have been calculated.

On the molecular structures of (545)macrotricyclic chelates in the M(II) ion-2,3-butanedione-aminomethanamidine ternary systems

The geometric parameters of the molecular structures of macrotricyclic M(II) complexes with a tetradentate chelating ligand with the (NOON) coordination of donor sites formed by the template reactions in the M(II)-2,3-butanedione (H3C-C(=O)-C(=O)-CH3)-aminomethanamidine (H2N-C(=NH)-NH2) systems have been calculated by the OPBE/TZVP density functional theory (DFT) method. The bond lengths and bond and torsion angles in the resulting complexes have been reported. The enthalpies and Gibbs energies for the reaction of their formation have also been calculated. A conclusion has been drawn that template synthesis in these systems can be realized only upon complex formation in a gelatin-immobilized matrix.