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1.
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.  相似文献   

2.
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.  相似文献   

3.
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.  相似文献   

4.
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.  相似文献   

5.
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.  相似文献   

6.
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.  相似文献   

7.
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.  相似文献   

8.
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.  相似文献   

9.
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.  相似文献   

10.
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.  相似文献   

11.
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 Δf H 298o and a standard Gibbs energy, Δf G o for all complexes studied are positive.  相似文献   

12.
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.  相似文献   

13.
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.  相似文献   

14.
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.  相似文献   

15.
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).  相似文献   

16.
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.  相似文献   

17.
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.  相似文献   

18.
Conditions for the preparation of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) 4-methylphthalates were investigated and their composition, solubility in water at 295 K and magnetic moments were determined. IR spectra and powder diffraction patterns of the complexes prepared with molar ratio of metal to organic ligand of 1.0:1.0 and general formula: M [ CH3C6H3(CO2)2nH2o (n=1-3) were recorded and their decomposition in air were studied. During heating the hydrated complexes are dehydrated in one (Mn, Co, Ni, Zn, Cd) or two steps (Cu) and next the anhydrous complexes decompose to oxides directly (Cu, Zn), with intermediate formation of carbonates (Mn, Cd), oxocarbonates (Ni) or carbonate and free metal (Co). The carboxylate groups in the complexes studied are mono- and bidentate (Co, Ni), bidentate chelating and bridging (Zn) or bidentate chelating (Mn, Cu, Cd). The magnetic moments for paramagnetic complexes of Mn(II), Co(II), Ni(II) and Cu(II) attain values 5.92, 5.05, 3.36 and 1.96 M.B., respectively. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

19.
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.  相似文献   

20.
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.  相似文献   

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