Molecular structures of (454)macrotricyclic chelates in the M(II) ion–thiosulfate anion–ethylenediamine systems according to quantum-chemical DFT calculations

The geometric parameters of the molecular structures of (454)macrotricyclic M(II) complexes with a tetradentate chelating ligand with the (NSSN)-coordination of donor sites formed by the template reactions in the M(II)–thiosulfate anion S₂O₃^2-–ethylenediamine H₂N–CH₂–CH₂–NH₂ have been calculated by the hybrid OPBE/TZVP density functional theory (DFT) method. The standard enthalpies, standard entropies, and standard Gibbs energies of formation of these complexes have been calculated, and a conclusion has been drawn that the template synthesis in these systems is possible when carrying out appropriate reactions under common conditions (in solution of solid phase).     

Molecular structure of the macrocyclic copper(II) chelate with 6,7,13,14-tetramethyl-3,10-dithio-1,2,4,5,8,9,11,12-octaazatetradecatetraene-1,5,7,11 according to quantum-chemical DFT calculations

The key parameters of the molecular structure of macrotetracyclic (NNNN)-coordinated chelate of Cu(II) with 6,7,13,14-tetramethyl-3,10-dithio-1,2,4,5,8,9,11,12-octaazatetradecatetraene-1,5,7,11 have been calculated by means of the DFT-based B3LYP6-31G(d) method in GAUSSIAN-09 software. The complex may be formed via self-assembly of Cu(II), thiocarbohydrazide, and diacetyl in the gelatin-immobilized matrix implants. The bond lengths, bond angles, and torsion angles are presented; it has been shown that the metal chelate and the chelating ligand are almost planar.     

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.     

Specifics of molecular structures of (565)macrotricyclic 3d-Metal chelates in the ternary systems M(II)-hydrazinecarbothioamide-2,4-Pentanedione according to DFT calculations

The geometric parameters of the molecular structures and thermodynamic parameters of formation of macrotricyclic M(II) complexes (M = Mn, Fe, Co, Ni, Cu, and Zn) with the MN₂S₂ coordination core formed by the reactions of corresponding hexacyanoferrates(II) with hydrazinecarbothioamide H₂N-HN-C(=S)-NH₂ and 2,4-pentanedione H₃C-C(=O)-CH₂-C(=O)-CH₃ in gelatin-immobilized matrix implants have been calculated by the B3LYP hybrid density functional theory method with the use of the 6-31G(d) basis set and the Gaussian 09 program package. The bond lengths and bond and torsion angles in these chelates have been reported. It has been shown that the Fe(II) and Ni(II) complexes are strictly planar, whereas the Mn(II), Co(II), and Cu(II) complexes are quasi-planar with a rather small deviation of the MN₂S₂ chelate core from coplanarity, and only the Zn(II) complex is pseudotetrahedral. The additional sixmembered chelate rings resulting from the above processes are almost planar in all chelates.     

Structure of (5656)macrotetracyclic chelates in the ternary systems M(II)-ethanedithioamide-acetone (M = Mn, Fe, Co, Ni, Cu, Zn) according to DFT calculations

The thermodynamic and geometric parameters of M(II) macrotetracyclic chelates (M = Mn, Fe, Co, Ni, Cu, and Zn) with the (NNNN) coordination of the donor ligand sites, formed by the complexation reactions of corresponding M(II) compounds, ethanedithioamide H₂N-C(=S)-C(=S)-NH₂, and acetone H₃C-C(=O)-CH₃ in gelatin-immobilized matrix implants have been calculated by the OPBE/TZVP density functional theory method with the use of the Gaussian 09 program package. The bond lengths and bond and torsion angles in these complexes have been reported. It has been shown that despite the fact that the MN₄ chelate core in them is almost planar, the five- and six-membered chelate rings are pronouncedly non-coplanar. In the Mn(II), Fe(II), Co(II), and Ni(II) complexes, these chelate rings are pairwise identical, whereas in the Cu(II) and Zn(II) complexes, they are noticeably different.     

Molecular structures of macrotricyclic 4<Emphasis Type="Italic">d</Emphasis> M(II) chelates with the (NNNN)-donor ligand 2,7-dithio-3,6-diazaoctadiene-3,5-dithioamide-1,8 according to quantum-chemical density functional theory calculations

The thermodynamic and geometric parameters of the molecular structures of macrotricyclic Mo(II), Ru(II), Rh(II), Pd(II), Ag(II), and Cd(II) complexes with the tetradentate ligand 2,7-dithio-3,6-diazaoctadiene-3,5-dithioamide-1,8 with the (NNNN) coordination of the donor centers have been calculated by the hybrid density functional theory (DFT) method in the OPBE/TZVPQZP approximation with the use of the Gaussian09 program package. The Pd(II), Ag(II), and Cd(II) complexes are exactly planar, the Tc(II) and Rh(II) complexes exhibit slight deviations from coplanarity, while the Mo(II) and Ru(II) complexes have rather significant deviations. The five-membered chelate rings in the complexes are either strictly planar or deviate slightly (no more than by 5°) from coplanarity.     

Molecular structures of (555)macrotricyclic chelates appearing in 3d-element(ii) ion-hydrazinomethanethioamide-ethanedial systems according to density functional theory calculations

Thermodynamic and geometric parameters have been calculated using the hybrid density functional theory method B3LYP with the 6-31G(d) basis set and the Gaussian03 program for the macrotricyclic complexes of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) with an (NSSN)-coordinated ligand that can result from the complexation of metal hexacyanoferrates(II) with hydrazinomethanethioamide H₂N-HN-C(=S)-NH₂ and ethanedial HC(=O)-CH(=O) in gelatin-immobilized matrix implants. Bond lengths and valence and torsion angles in these complexes are reported. The Ni(II) and Cu(II) complexes are practically planar. The Mn(II), Fe(II), and Co(II) complexes are characterized by a small deviation from coplanarity, and the Zn(II) complex is noticeably noncoplanar. The additional five-membered metallacycle resulting from template ??joining?? is nearly planar in all complexes.     

Geometric parameters and energies of molecular structures of macrocyclic metal chelates in the ternary 3<Emphasis Type="Italic">d</Emphasis> 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.     

Comparative stability of isomeric (565)macrotricyclic chelates of 3d-elements formed in the systems M(II)-thiosemicarbazide-formaldehyde according to DFT B3LYP data

Comparative stability of three types of (565)macrotricyclic chelates of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) with chelate nodes MN₂S₂ and MN₄ have been analyzed by means of hybrid density functional method B3LYP with the 6-31G(d) basis set using GAUSSIAN-09 software. These chelates may potentially be formed in template interaction between gelatin-immobilized hexacyanoferrate(II) of respective metal ions M(II), thiosemicarbazide H₂N-HN-C(=S)-NH₂, and formaldehyde H₂C=O. It has been demonstrated that for all M(II) considered, the complex with chelate nodes MN₂S₂ is more stable. Key structural parameters of the complexes (bond lengths, bond and torsion angles) are presented. It is noted that pseudotetrahedral coordination of ligand donor centers around M(II) is typical for Mn(II), Co(II), Cu(II), and Zn(II), whereas for Fe(II) and Ni(II) it is almost planar. Values of standard enthalpy ΔH _f,298 ⁰ and standard Gibbs energy ΔG _f,298 ⁰ are positive for nearly all the complexes studied.     

Mutual stability and molecular structures of asymmetric (555)macrotricyclic 3d-metal chelates formed by self-assembly in M(II) ion-ethanedithioamide-hydrazinomethanethioamide-2-oxopropanal quaternary systems according to density functional theory calculations

The thermodynamic and geometric parameters of asymmetric macrotricyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the NSSN-coordination of donor sites of the ligand that can form upon complexation of the corresponding hexacyanoferrates(II) by ethanedithioamide H₂N-C(=S)-C(=S)-NH₂, hydrazinomethanethioamide H₂N-NH-C(=S)-NH₂, and 2-oxopropanal in gelatin-immobilized matrices have been calculated by the OPBE/TZVP nonhybrid DFT method with the use of the Gaussian09 program package.     

Stability of isomerous chelates in M(II)-thiocarbamoylmethanamide-ethandial systems according to the DFT B3LYP method (M = Mn, Fe, Co, Ni, Cu, Zn)

Calculations of the optimal geometry and standard thermodynamic parameters of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) isomerous macrotricyclic complexes with MN₂O₂, MN₂S₂, and MN₄ chelate bonds, which can in principle appear as a result of template processes between gelatine-immobilized hexacyanoferrates (II) of corresponding M(II) metal ions, thiocarbamoylmethaneamide (thiooxamide) H₂N-C(=S)-C(=O)-NH₂, and ethanedial HC(=O)-CH(=O), were performed according to the B3LYP hybrid density functional method using a 6-31G(d) basis set with the Gaussian 98 program. It was found that of all of the considered M(II), the most stable are complexes with MN₄ chelate bonds, where the values of a standard enthalpy Δ_f H ₂₉₈^o and a standard Gibbs energy, Δ_f G ^o for all complexes studied are positive.     

Quantum-chemical calculation of the molecular structures of 3d metal chelates with ligands self-assembled in the M(II)-hydrazinomethane thiohydrazide-acetone systems

The geometric parameters of M(II) complexes (M = Mn, Fe, Co, Ni, Cu, and Zn) with chelating ligands 1-hydrazino-4,6,6,12-tetramethyl-2,3,7,8,10,11-hexaazatridecatetraene-1,3,8,11-dithiol-1,9 and 2,8,8,10,16-pentamethyl-3,4,6,7,11,12,14,15-octaazaheptadecapentaene-2,5,10,12,15-dithiol-5,13 with the NNSS coordination self-assembled in the M(II)-hydrazinomethane thiohydrazide-acetone systems 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, in the complexes formed by the same M(II) ion, these characteristics are close to each other. For all M(II) ions under consideration, an additional six-membered chelate ring resulting from template cross-linking is turned to the two five-membered rings and is nonplanar as distinct from the latter.     

Molecular structures of metalmacrocyclic chelates of 3d-elements formed at template synthesis in the ion M(II)- thiooxamide-guanidine-formaldehyde quaternary systems

Using density functional theory (DFT) at the OPBE/TZP level, the calculation of the geometric parameters of the molecular structures of M(II) (5456)macrotetracyclic complexes with a tetradentate macrocyclic ligand with (NNNN)-coordination of donor centers, resulting from template reactions in M(II)- thiooxamide- guanidine-formaldehyde quaternary systems, where M= Mn, Fe, Co, Ni, Cu, Zn was performed. The calculation of the molecular structure of this “template” ligand itself was also carried out. The values of the bond lengths, bond and torsion angles in the resulting complexes are presented. The values of the standard enthalpy, entropy and Gibbs free energy of formation of these compounds were also calculated.      

(5656)Macrotetracyclic chelates of doubly charged 3d-element ions with 1,4,8,11-tetraazacyclotetradecane-2,3,9,10-tetrathione and their molecular structures according to density functional theory data

The OPBE/TZVP density functional theory (DFT) calculations were performed to study the molecular structures of (5656)macrotetracyclic M(II) complexes with a tetradentate ligand with (NNNN)-coordination of the donor sites formed upon template reactions in the M(II)-dithiooxamide-propane-1,3-diol ternary systems (M = Mn, Fe, Co, Ni, Cu, Zn). The bond lengths and bond angles for the resulting complexes are presented. The standard enthalpy, entropy, and Gibbs energy of formation of these compounds were calculated.     

The relative stability of macrotricyclic metal complexes in M(II)-thiocarbohydrazide-acetone (M = Mn, Fe, Co, Ni, Cu, Zn) ternary systems according to the data of quantum-chemical calculations

The B3LYP hybrid method of density functional theory with the 6–31G(d) basis set was used to calculate the optimum geometry and standard thermodynamic parameters of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) macrotricyclic complexes with MN₂S₂ and MN₄ chelate nodes. The calculations were performed using the Gaussian 98 package. Such complexes could in principle appear because of temperature processes between gelatin-immobilized hexacyanoferrates(II) of the corresponding M(II) metal ions, thiocarbohydrazide, and acetone. For all the M(II) metals considered, complexes with MN₂S₂ chelate nodes were stablest. The standard Gibbs energies Δ_f G ₂₉₈^° values were positive for all the complexes specified.     

Ternary complexes of 3d metal(II) ions with acetylacetone and salicylaldoxime

Summary New ternary complexes of first-row transition metal ions of composition [M(salox)(acac)] [where M=VO^IV, Mn^II, Co^II, Cu^II and Zn^II, acacH=acetylacetone, saloxH=salicylaldoxime] and their bis-pyridine adducts have been prepared. Molar conductivity measurements indicate that the complexes are non-electrolytes, while magnetic and electronic spectral studies show an essentially octahedral stereochemistry except for the nickel(II) complex which exhibits a square planar-octahedral equilibrium. The e.s.r. spectra show that the complexes are monomeric in CHCl₃ solution.     

Crystal and molecular structures of bis(2,2,6,6-tetramethyl-3-methylaminoheptan-5-onate) copper(II) and nickel(II)

Two bis-chelates M(tmih)₂ (M = Cu(II), Ni(II), tmih = (CH₃)₃C(NCH₃)CHCOC(CH₃)₃)^? are synthesized and their crystal structures are determined using XRD (Bruker APEX-II diffractometer with a CCD detector, λMoK _α, λCuK _α, graphite monochromator, T = 240(2) K and 296(2) K): Cu(tmih)₂ (I) (space group P2₁/c, a = 12.9670(8) Å, b = 18.4921(9) Å, c = 11.0422(6) Å, β = 93.408(4)°, V = 2643.1(3) ų, Z = 4) and Ni(tmih)₂ (II) (space group P2₁/c, a = 12.810(2) Å, b = 18.529(2) Å, c = 11.243(2) Å, β = 91.959(7)°, V = 2667.1(6) ų, Z = 4). The complexes are isostructural; the coordination polyhedron of metal atoms is a flattened tetrahedron formed from two O atoms (Cu-O of 1.901(2) Å, 1.892(2) Å, Ni-O of 1.845(2) Å, 1.833(2) Å) and two N atoms (Cu-N of 1.976(3) Å, 1.972(3) Å, Ni-N of 1.911(2) Å, 1.920(2) Å) of the ligand; the chelate OMN angles (M = Cu(II), Ni(II)) are in the 87.4–93.1° range; the OMO and NMN angles are 162.2° and 167.2° in I, 171.1° and 173.2° in II. The complexes have the molecular structures formed from isolated molecules bonded by van der Waals interactions. Using a quantum chemical hybrid M06 method, the structures of copper(II) chelates with the H, CH₃, CH₂CH₃, CH(CH₃)₂, and C(CH₃)₃ substituents at the nitrogen atom are calculated. Found that with a bulky substituent at the nitrogen atom, the formation of chelates is hindered due to the intraligand repulsion between the atoms of this substituent and the tert-butyl group.     

Hetero-binuclear chelates of Mn(II), Co(II) and Cu(II) o-cresolphthalein complexonates with other metal ions

Heterobinuclear metal chelates of Mn²⁺, Co²⁺ or Cu²⁺ and some transition metal ions with o-cresolphthalein complexone have been prepared and characterized. Elemental analyses are in agreement with proposed formulae. Thermal analyses (TGA and DTA) were used to determine the degradation products; some thermodynamic parameters were calculated. IR and UV-Vis spectra identified the mode of bonding between the metal ions and the ligand as well as its geometry. Magnetic moment determination and ESR spectra of the heterobinuclear complex revealed some antiferromagnetic interaction between the metal ions, which depends mainly on the two metal ions forming the chelate. Electrochemical studies of the complexes [DC-polarography and cyclic voltammetry (CV)] confirmed the existence and the nature of the metal ions in the chelate.     

New oxamidato-bridged Cu(II)-Ni(II) complexes: supramolecular structures with thiocyanate ligands and hydrogen bonds. Magnetostructural studies: DFT calculations

Four new supramolecular compounds of Cu(II)-Ni(II) have been synthesized and characterized: [Cu(Me(2)oxpn)Ni(mu-NCS)(H(2)O)(tmen)](2)(ClO(4))(2) (1), [Cu(Me(2)oxpn)Ni(mu-NCS)(H(2)O)(tmen)](2)(PF(6))(2) (2), [Cu(oxpn)Ni(mu-NCS)(NCS) (tmen)](n) (3), and [Cu(Me(2)oxpn)Ni(mu-NCS)(NCS)(tmen)](n) (4), where oxpn = N,N'-bis(3-aminopropyl)oxamidate, Me(2)oxpn = N,N'-bis(3-amino-2,2'-dimethylpropyl)oxamidate, and tmen = N,N,N',N'-tetramethylethylenediamine. Their crystal structures were solved. Complexes 1 and 2 have the same tetranuclear cationic part but a different counteranion. The cationic part consists of two [Cu(Me(2)oxpn)Ni] moieties linked by SCN(-) bridged ligands and intra-tetranuclear hydrogen bonds. In the case of complex 3, a two-dimensional system was built, the thiocyanate ligand linking the dinuclear units gives a chain, and the chains are linked together by hydrogen bonds; intrachain hydrogen bonds are also present. For complex 4, the thiocyanate ligands produce intermolecular linkages between the dinuclear entities, giving a one-dimensional system; intrachain hydrogen bonds are also present. The magnetic properties of the four complexes were studied by susceptibility measurements vs temperature. DFT calculations were made to study the contribution of the SCN(-) and hydrogen bond bridges in the magnetic coupling.     

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.