Models of Molecular Structures of “Template” (5676)Macrotetracyclic 3<Emphasis Type="Italic">d</Emphasis> M(II) Chelates with a 16-Membered Macrocyclic Ligand according to Density Functional Theory Data

The geometries of (5676)macrotetracyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the (NNNN) coordination of the chelant donor sites, formed through template processes in the M(II)–3,3,8,8-tetramethyl-4,7-diazadecanedihydrazone-1,10-butanedione-2,3 systems have been calculated by the DFT OPBE/TZVP method with the Gaussian 09 program package. The bond lengths and angles and selected nonbonded angles in these complexes with the MN₄ chelate core have been determined. It has been demonstrated that none of the chelate rings is planar: the smallest deviation from coplanarity is always observed for the five-membered rings and the largest, for the six-membered rings not identical to each other. The seven-membered ring resulting from the template cross-linking exhibits deviations from coplanarity intermediate between those for the five- and six-membered rings.     

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.     

DFT B3LYP calculation of the spatial structure of Co(II), Ni(II), and Cu(II) template complexes formed in ternary systems metal(II) ion-dithiooxamide-formaldehyde

The hybrid density functional theory B3LYP method with the 6-31G(d) basis set and the Gaussian 98 program has been used for calculating the geometric parameters of the Mn(II), Co(II), Ni(II), and Cu(II) complexes with NNSS-donor macrocyclic ligands forming in the course of template processes in the M(II)-dithiooxamide-formaldehyde systems. The bond lengths and bond angles in the complexes with the MN₂S₂ metal chelate core are reported. For all M(II) ions, the extra six-membered chelate ring that form as a result of template assembly is rotated through a rather large angle with respect to two five-membered rings and the ring itself is not planar.     

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.     

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.     

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.     

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.     

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.     

DFT quantum-chemical calculations of molecular structures for template heteroligand (5757)macrocyclic M(II) chelates of 3<Emphasis Type="Italic">d</Emphasis> elements with a 16-membered macrocyclic ligand and Br<Superscript>–</Superscript> ions

The geometric parameters of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) (5757)macrocyclic complexes with the NSSN-coordination of the donor sites of the chelant, which can be generated in template processes in M(II)–N-methylthiocarbohydrazide–hexanedione-2,5 systems and in the subsequent reaction of the newly formed metal chelate with 1,2-di(bromomethyl)benzene, have been calculated by the OPBE/TZVP functional density theory (DFT) hybrid method using the Gaussian09 program package. The 5-membered chelate ring is strictly planar in none of the complexes,. In all complexes (except for the Co(II) complex), 5-membered chelate rings are identical to each other. Both 7-membered chelate rings generated by the template links have a pronounced non-coplanarity. The bond angles between M–Br bonds are not 180° in any one of the complexes studied, although approaching this value.     

Molecular structures of (575)macrotricyclic 3<Emphasis Type="Italic">d</Emphasis>-metal chelates in M(II)–N-methylthiocarbohydrazide–hexanedione-2,5 according to density functional theory calculations

The geometric parameters of the molecular structures and thermodynamic parameters of macrotricyclic M(II) (M = Mn, Fe, Co, Ni, Cu, Zn) complexes with an MN₂S₂ chelate core formed by the template reactions of the M(II) with N-methylthiocarbohydrazide H₃C–HN–HN–C(=S)–NH–NH₂ and hexanedione- 2,5 H₃C–C(=O)–CH₂–CH₂–C(=O)–CH₃ have been calculated by the DFT method with the Gaussian09 program package. The bond lengths, bond angles, and some nonbonded angles in these complexes have been determined. In all the complexes, the M(II) central ion is pseudotetrahedrally coordinated by the donor atoms of an inner-sphere tetradentate ligand; the (N₂S₂) group of the donor atoms is not planar. The additional seven-membered chelate rings show significant deviations from coplanarity (>60°). The noncoplanatiry of the five-membered rings is less pronounced.     

Models of molecular structures of macrocyclic metal chelates in the ternary 4<Emphasis Type="Italic">d</Emphasis> M(II) ion–ethanedithioamide–ethanedial systems according to quantum-chemical DFT calculations

The thermodynamic and geometric parameters of the molecular structures of macrotricyclic Tc(II), Ru(II), Rh(II), Pd(II), Ag(II), and Cd(II) complexes with the (NSSN)-coordination of the ligand donor sites formed by complexation of the corresponding M(II) ions with ethanedithioamide H₂N–C(=S)–C(=S)–NH₂ and ethanedial HC(=O)–CH(=O) have been calculated by the OPBE/TZVPQZP hybrid density functional theory method with the use of the Gaussian09 program package. The bond lengths and bond angles in these complexes have been reported, and it has been stated that the Rh(II) and Ag(II) complexes are nearly planar, the Tc(II), Pd(II), and Cd(II) complexes are slightly nonplanar, while the Ru(II) complex exhibits a rather considerable deviation from coplanarity. The additional five-membered chelate ring resulting from template cross-linking is either strictly planar (in the Tc(II), Rh(II), Pd(II), and Ag(II) complexes) or nearly planar (in the Ru(II) and Cd(II) complexes).     

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.     

Structures of platinum(II) complexes of 2-aminomethylaziridine and S-2-aminomethylazetidine and correlation of anticancer activities of (2-aminomethylazacycloalkane)platinum(II) complexes with the geometry of the chelate rings formed with platinum(II)

The spectroscopic properties of platinum(II) complexes with 2-aminomethyl-derivatives of small-membered 1-aza-cycloalkane, i.e., =2-aminomethylaziridine=azida and S-2-aminomethylazetidine=S-azeda, and the crystal structures of their dichloro complexes demonstrate that the conformation of the fused three- (azida) or four- (S-azeda) and five-membered chelate ring formed by the coordination of S-azida and S-azeda to platinum(II) has an S(N) absolute configuration at the secondary amine site and that the two alkyl groups extend axially from the five-membered chelate ring. The chelate ring of the azida is more planar than the S-azeda or other 2-aminomethyl-1-azacycloalkanes. The anticancer activity reported for azeda and 2-aminomethylpyrrolidine appears to be related to their coordination structure, namely the presence of cis-fused successive rings.     

Quantum-chemical modeling of the molecular structures of (555)macrotricyclic chelates in M(II) ion–thiooxamide–glyoxal ternary systems (M = Mn,Fe, Co,Ni, Cu,Zn)

The thermodynamic and geometric parameters of isomeric macrotricyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes that can form upon the complexation of the corresponding hexacyanoferrates( II) with thiooxamide H₂N–C(=S)–C(=O)–NH₂ and glyoxal HC(=O)–CH(=O) in gelatin-immobilized matrices have been calculated by the OPBE/TZVP DFT method with the use of the Gaussian09 program package. It has been found that a complex with the MN₄ chelate core is most stable for M = Mn, Fe, Co, Ni, and Zn, and the MN₂S₂ core is most stable for M = Cu. Bond lengths and bond angles have been reported, and it has been noted that in all complexes, except the Zn(II) one, the chelate core and three fivemembered chelate rings are almost planar.     

Quantum chemical calculation of the molecular structures of (666)macrotricyclic chelates of 3D elements in the M(II)-propanedithioamide-formaldehyde systems by the density functional theory method

The nonhybrid OPBE/TZVP density functional theory (DFT) method and the Gaussian09 program package were used to calculate the thermodynamic and geometric parameters of asymmetric macrocyclic M(II) complexes with three six-membered metal rings and (NNNN)-coordination of the donor sites of the ligand. The complexes are formed upon self-assembly (template synthesis) of hexacyanoferrates(II) of the corresponding M(II), propanedithioamide H₂N-C(=S)-CH₂-C(=S)-NH₂, and formaldehyde H₂C(=O) in gelatin-immobilized matrix implants. Note that complexes of this type are formed only for M = Ni, Cu, and Zn, while for M = Mn, Co, and Fe, these compounds are unstable. Bond lengths and bond and torsion angles are presented. In each of these complexes, both the MN₄ chelate units and the N₄ units and all sixmembered metal rings were found to be non-coplanar.     

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.     

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.     

Heterobimetallische Komplexe mit Chelatliganden aus mehrzähnigen Aminen und 1,1-Bis(diphenylphosphan)ethen

Heterobimetallic Complexes with Chelate Ligands from Multidentate Amines and 1,1-Bis(diphenylphosphine)ethene By an addition reaction of bidentate amines Me₂N(CH₂)_nNH₂ (n = 2, as-4C2N; 3, as-5C2N) and vinylidene derivatives with an activated double bond CH₂ = C(PPh₂)₂M(CO)₄ (M = Cr, Mo, W) were synthesized in dichlormethane unsymmetrical chelate ligands of the type as-4C2N (or as-5C2N)PPM(CO)₄. They gave with divalent salts M′Y₂ (Y = ac, M′ = Cu, Ni. Y = Cl, M′ = Zn, Cd, Hg) the coloured bimetallic complexes M′Y(as-4C2N) (or as-5C2N)PPM(CO)₄ which were characterized by means of IR-, UV/VIS spectroscopic and ¹H, ¹³C and ³¹P NMR measurements. The molecular structures of the complexes Cuac₂(as-5C2N)PPCr(CO)₄, I and that of CdCl₂(as-4C2N)PPCr(CO)₄, II , were acertained by results of single crystal X-ray determinations. In the crystals of I—II , the coordination polyhedron of each chromium(0) central atom containing two phosphorous donor atoms in a four-membered chelate ring and four terminal CO ligands is octahedrally distorted. This coordination sphere is connected at the carbon ring atom via a methylen chain group (spacer) with the bidentate amine ligand, which has a secondary and a tertiary nitrogen donor atom. Both nitrogen atoms are coordinated with the Cuac₂ under formation of a new kind of [4 + 2]-coordination in a trischelate complex. The six-membered diamine chelat ring in I has a chair-like conformation. The chromium-cadmium complex II is dimer from which the Cd central atoms obtain the rare coordination number of five. The related five-membered diamine chelate ring has δ conformation.     

Molecular structures of (5656)macrotetracyclic chelates in M(II) ion–ethanedithioamide–methanimine–hydrogen cyanide quaternary systems by DFT calculations

The geometric parameters of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) (5656)macrotetracyclic complexes with the NNNN-coordination of the donor cites of the chelant, which can be formed upon template processes in M(II)–ethanedithioamide–methanimine–hydrogen cyanide quaternary systems, have been calculated using the density functional (DFT) hybrid method in the OPBE/TZVP approximation with the use of the Gaussian09 program package. It is shown that no one of the 5-membered chelate rings is planar, and these rings are not identical in the complexes studied. The 6-membered chelate rings are likewise not identical: one has a prominent noncoplanarity, and the other is almost planar. In all metal complexes, the nitrile nitrogen atom in one 6-membered ring noticeably departs from the plane of the ring, and in the other 6-membered ring, the respective nitrogen atom lies virtually in the plane of the ring.     

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.