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 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.     

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.     

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.     

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.     

Structural Changes in the Macrocycles of Tetrathioand Dithiodioxo-Substituted 1,8-Dioxa-3,6,10,13-tetraazacyclotetradecane Caused by Complexation with 3<Emphasis Type="Italic">d</Emphasis> M(II) Ions according to Quantum-Chemical DFT Calculation

The bond angles in the macrocycles of tetrathio- and dioxodithio-substituted 1,8-dioxa-3,6,10,13-tetraazacyclotetradecanes and their Cr(II), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the (NNNN) coordination of the ligand donor sites, formed upon the complexation in the ternary systems M(II)–ethanedithioamide H₂N–C(=S)–C(=S)–NH₂ (thiocarbamoylmethanamide H₂N–C(=S)–C(=O)–NH₂)–formaldehyde H₂C(=O) in gelatin-immobilized matrix implants have been calculated by the DFT OPBE/TZVP method with the Gaussian 09 program package. It has been stated that, depending on the nature of M(II) and macrocyclic ligand, the complexation can lead to both the decrease and the increase in the degree of macrocycle distortion (quantatively characterized as the degree of deviation of the macrocycle from coplanarity).     

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.     

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.     

Molecular structures of (5454) macrotetracyclic chelates of 3d M(II) ions with 4,5,9,10-tetramethyl-1,3,6,8-tetraaza-5,8-cyclodecadiene-2,7-diimine according to DFT quantum-chemical calculations

The molecular structures of (5454)macrotetracyclic M(II) complexes with the tetradentate ligand with the (NNNN)-coordination of donor sites formed by the template reactions in the ternary systems M(II)-aminomethanamidine (H₂N-C(=NH)-NH₂)-3-hydroxy-2-butanone H₃C-C(=O)-C(OH)-CH₃), where M = Mn, Fe, Co, Ni, Cu, and Zn, have been calculated by the OPBE/TZVP density functional theory (DFT) method. The bond lengths and bond and torsion angles in the complexes, as well as the standard enthalpies, entropies, and Gibbs energies of formation of these compounds, are reported.     

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.     

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.     

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.     

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.     

New complexes of some d-electron elements with 3-methyladipic acid

Conditions for the preparation of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) 3-methyladipates were investigated and their qualitative composition and magnetic moments were determined. The IR spectra and powder diffraction patterns of the complexes prepared of the general formula M(C₇H₁₀O₄)·nH₂O (n=0-11) were recorded and their thermal decomposition in air were studied. During heating the hydrated complexes are dehydrated in one (Co, Ni) or two steps (Mn, Zn) losing all crystallization water molecules (Co, Ni) or some water molecules (Mn, Zn) and then anhydrous (Co, Ni, Cu) or hydrated complexes (Mn, Zn) decompose directly to oxides (Mn, Co, Zn) or with intermediate formation the mixture of M+MO (Ni, Cu). The carboxylate groups are bidentate (Mn, Co, Ni, Cu) or monodentate (Zn). The complexes exist as polymers. The magnetic moments for the paramagnetic complexes of Mn(II), Co(II), Ni(II) and Cu(II) attain values 5.48, 4.49, 2.84 and 1.45 B.M., respectively. This revised version was published online in July 2006 with corrections to the Cover Date.     

Spectral, magnetic and biological studies of 1,4-dibenzoyl-3-thiosemicarbazide complexes with some first row transition metal ions

The ligand 1,4-dibenzoyl-3-thiosemicarbazide (DBtsc) forms complexes [M(DBtsc-H)(SCN)] [M = Mn(II), Co(II) or Zn(II)], [M(DBtsc-H) (SCN)(H₂O)] [M = Ni(II) or Cu(II)], [M(DBtsc-H)Cl] [M = Co(II), Ni(II), Cu(II) or Zn(II)] and [Mn(DBtsc)Cl₂], which have been characterized by elemental analyses, magnetic susceptibility measurements, UV/Vis, IR,¹H and¹³C NMR and FAB mass spectral data. Room temperature ESR spectra of the Mn(II) and Cu(II) complexes yield <g> values, characteristic of tetrahedral and square planar complexes respectively. DBtsc and its soluble complexes have been screened against several bacteria, fungi and tumour cell lines.     

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.     

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.     

Formation of 1 D and 3 D coordination polymers in the solid state induced by mechanochemical and annealing treatments: bis(3-cyano-pentane-2,4-dionato) metal complexes

Bis(3-cyano-pentane-2,4-dionato) (CNacac) metal complex, [M(CNacac)(2)], which acts as both a metal-ion-like and a ligand-like building unit, forms supramolecular structures by self-assembly. Co-grinding of the metal acetates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) with CNacacH formed a CNacac complex in all cases: mononuclear complex was formed in the cases of Mn(II), Cu(II) and Zn(II), whereas polymeric ones were formed in the cases of Fe(II), Co(II) and Ni(II). Subsequent annealing converted the mononuclear complexes of Mn(II), Cu(II) and Zn(II) to their corresponding polymers as a result of dehydration of the mononuclear complexes. The resultant Mn(II), Fe(II), Co(II), Ni(II) and Zn(II) polymeric complexes had a common 3 D structure with high thermal stability. In the case of Cu(II), a 1 D polymer was obtained. The Mn(II), Cu(II) and Zn(II) polymeric complexes returned to their original mononuclear complexes on exposure to water vapour but they reverted to the polymeric complexes by re-annealing. Co-grinding of metal chlorides with CNacacH and annealing of the mononuclear CNacac complexes prepared from solution reactions were also examined for comparison. [Mn(CNacac)(2)(H(2)O)(2)], [M(CNacac)(2)(H(2)O)] (M=Cu(II) and Zn(II)) and [M(CNacac)(2)](infinity) (M=Mn(II), Fe(II) and Zn(II)) are new compounds, which clearly indicated the power of the combined mechanochemical/annealing method for the synthesis of varied metal coordination complexes.     

Magnetic and EPR properties of Mn(II), Fe(III), Ni(II) and Cu(II) complexes of thiosemicarbazone of α-hydroxy-β-napthaldehyde

Mn(II), Fe(III), Ni(II) and Cu(II) complexes of the thiosemicarbazones of α-hydroxy-β-naphthaldehyde have been isolated. Ni(II) complex is diamagnetic, Cu(II) is planar involving metal-metal interactions, Mn(II) complex (μ_eff = 3.86B.M) has been assigned a planar structure with S = 3/2 while Fe(III) complex is five coordinated with S = 3/2.