The effect of chemical modification of the macrocycle on the complex formation between porphyrins and metal salts in organic solvents

The complex formation of β-octaethylporphyrin, β-octaethyl-meso-monophenylporphyrin, β-octaethyl-meso-tetraphenylporphyrin, meso-diphenylporphyrin, meso-triphenylporphyrin, and meso-tetraphenylporphyrin with Zn(II), Cu(II), Co(II), and Mn(II) acetates and chlorides in dimethylformamide, dimethylsulfoxide, pyridine, acetic acid, and a chloroform–methanol 1 : 1 mixture has been studied by means of spectrophotometry. The observed regulations are in line with the concept of chemical reactivity of the N–H bonds in porphyrins of different complexity.     

Specific Features of the Structure of Chelate Complexes of <Emphasis Type="Italic">N</Emphasis>-Thiocarbamoylamidophosphates with Zn(II) and Cd(II) Cations

The reaction of potassium salts of N-thiocarbamoylamidophosphates RC(S)NHP(O)(OPr-i)₂X [X = PhNH, p-MeOPhNH, p-BrPhNH, i-PrNH, t-BuNH, Et₂N, C₅H10N, OC₄H₈N, C₆H₁₁NH] with Zn(II) cation gives complexes of the composition Zn(L-O,S)₂. The Cd(II) complexes could not be isolated under analogous conditions because of their hydrolytic lability. The reaction of thioureas (X = PhNH, p-MeOPhNH) with Cd(II) acetate in DMF provides stable solvato complexes of the composition Cd(DMF)₂L₂. The structure of the resulting compounds was studied by means of IR, ¹H, and ³¹P NMR spectroscopy and EI and ESI mass spectrometry.     

Synthesis and spectral properties of sandwich <Emphasis Type="Italic">meso</Emphasis>-tetramethyltetrabenzoporphyrin-phthalocyanine complexes with lutetium,erbium, yttrium,and lanthanum

The reaction of phthalimide with zinc(II) propanoate gave meso-tetramethyltetrabenzoporphyrinatozinc(II) whose demetalation afforded the corresponding free base. The latter was used to synthesize complexes with lutetium, erbium, yttrium, and lanthanum. Heating of these complexes with excess phthalonitrile led to the formation of sandwich meso-tetramethyltetrabenzoporphyrin-phthalocyanine complexes. Spectral properties of the resulting compounds were studied.     

Thermal stability of <Emphasis Type="Italic">meso</Emphasis>-substituted metal corroles in inert and oxidative media

The thermal stability of 5,10,15-triphenylcorrole as the simplest representative of meso-substituted corroles and its complexes with d-metals (Cu³⁺, Mn³⁺, Mn⁴⁺, Co³⁺, Co⁴⁺, and Zn²⁺) is studied for the first time via thermogravimetry in oxidizing and inert atmospheres. It is shown that corroles, both as free ligands and in the form of metal complexes, are less thermally stable than porphyrins with a similar structure. It is found that if the free ligands of porphyrins are thermally more stable with respect to thermal oxidation than d-metal complexes, the thermal stability of metal corroles can be both lower and higher than those of free ligands. It is concluded that the order of thermal stability of compounds MnCor < CoCor < H₃Cor < ZnCorH < CuCor is reversed upon moving from an oxidizing to an inert medium. It is shown that corroles complexes with many d-metals (Co, Mn, and others) readily participate in extracoordination reactions with electron-donating solvents, e.g., DMF, as is indicated by spectrophotometry and thermogravimetry.     

Crystal structure and antitumor activities of a dinuclear cobalt(II) complex based on <Emphasis Type="Italic">meso</Emphasis>-1,2,3,4-tetra(1H-benzo[<Emphasis Type="Italic">d</Emphasis>]imidazol-2-yl)butane

The [Co₂(tbb)Cl₄]?4DMF complex, where tbb is meso-1,2,3,4-tetra(1H-benzo[d]imidazol-2-yl)butane, is synthesized and characterized by single crystal X-ray diffraction. For the complex: C₄₄H₅₄Co₂C_l4N₁₂O₄, M_r = 1074.65, monoclinic crystal system, space group P21/n, a = 9.2350(13) Å, b = 11.3566(15) Å, c = 23.879(3) Å, β = 90.547(2)°, V = 2504.3(6) ų, Z = 2, D_c = 1.425 g/cm³, λ = 0.71073 Å, μ(MoK_α) = = 0.929 mm^–1, F(000) = 1112, S = 1.047, R = 0.0765, and wR = 0.2110 for 13668 observed reflections with I > 2σ(I). It is a neutral dinuclear complex. One meso-1,2,3,4-tetra(1H-benzo[d]imidazol-2-yl)butane coordinates two cobalt(II) ions. Each cobalt(II) ion is formed by two tbb nitrogen atoms and two chloride ions. The antiproliferative activities of the complex are screened by MTT assay against Eca109 cancer cells. The complex exhibits inhibition on the growth of Eca109 cancer cells with IC₅₀ of 22.1±6.7 μM after 48 h treatment. The cobalt complex has potential application in treatment of Eca109 cancer. CCDC 1015791.     

Syntheses and Crystal Structures of Quinidinum-Zinc(II)-Trichloride and Quinidinum Iron(III) Tetrachloride Hydrogen Chloride Hydrate

A mononuclear coordination complex, quinidinum-zinc(II)-trichloride (I), and a multi-component ionic complex, quinidinum iron(III) tetrachloride hydrogen chloride hydrate (II), have been synthesized and characterized by elemental analyses, IR spectra, and single crystal X-ray diffraction (CIF files nos. 1497628 (I) and 1497629 (II)). The weak hydrogen-bonding interactions exist in both complexes I and II. Both complexes crystallize in the chiral space groups with the absolute configuration. Complex I crystallizes in the orthorhombic space group P2₁2₁2₁ with a = 7.6651(6), b = 11.4923(9), c = 24.653(2) Å, and Z = 4. Complex II crystallizes in the monoclinic space group P2₁ with a = 6.6425(15), b = 18.660(4), c = 10.958(3) Å, β = 104.973(3), and Z = 2.     

Hydrogen-Bonding Interaction in a Complex of Amino Acid with <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Dimethylformamide Studied by DFT Calculations

Theoretical studies on hydrogen-bonded complexes between amino acids (glycine, alanine and leucine) and N,N-dimethylformamide (DMF) in gas phase have been carried out using density functional theory (DFT) and ab initio calculations at the B3LYP/6-311++G** and MP2/6-311++G** theory levels. The structures, binding energy, stretching frequency and bond characteristics of the mentioned complexes were calculated. The NH₂ and COOH groups of amino acids form different types of hydrogen bonds with the DMF molecule, as well as alkyl side chains. High binding energy suggests multiple hydrogen bonds present in one complex. The nearly linear OH???O and NH???O contacts are stronger than a conventional hydrogen bond interaction with their H???O separation between 1.74 and 2.14 Å. The weaker CH???O H-bond is also discussed as being a crucial interaction in biological systems involving amino acids. The formation of this interaction results in a blue shift in the CH stretching frequency.     

<Emphasis Type="Italic">meso</Emphasis>-octyl-substituted tetrabenzoazaporphines and their zinc complexes: Synthesis and spectra

Zinc complexes of meso-trioctyltetrabenzomonoazaporphine and trans- and cis-meso-dioctyltetrabenzodiazaporphine were prepared by the reaction of 1,3-diiminoisoindoline with excess capric acid in the presence of zinc oxide. The corresponding metal-free porphines were prepared by treatment of the metal complexes with sulfuric acid. The spectra of the azaporphyrins prepared were examined.     

Synthesis and spectral properties of <Emphasis Type="Italic">meso</Emphasis>-phenyltetrabenzoazaporphyrins containing triphenylmethyl groups

4-(p-Triphenylmethylphenoxy)isoindoline-1,3-diimine was synthesized starting from 4-(p-triphenylmethylphenoxy)phthalodinitrile obtained by the reaction of 4-nitrophthalodinitrile with 4-(triphenylmethyl)phenol. The former was reacted with phenylacetic acid in the presence of zinc oxide to obtain zinc complexes of meso-phenyltetrabenzoazaporphyrins containing triphenylmethyl groups. Spectral properties of the synthesized compounds were studied.     

Preparation,characterization and crystal structures of metal(II) tetraza macrocyclic complexes with organic co-ligands

The complexes [Ni(L1)(pyc)₂]·2H₂O (1) (L1 = C-meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane; Hpyc = pyrazinecarboxylic acid) and [Cu(L2)(H-cpdc)] (2) (L2 = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18,0^7.12]docosane; H₂-cpdc = cyclopropanedicarboxylic acid) have been synthesized and structurally characterized. The crystal structure of complex 1 shows a distorted octahedral coordination geometry around the nickel(II) center, with four secondary amines in the equatorial positions and two nitrogen atoms of the pyc^? ligands in the trans positions. In complex 2, the coordination environment around the copper(II) center is a Jahn–Teller distorted octahedron with four Cu–N bonds and two axial Cu–O bonds. The electronic spectra, electrochemical and TGA behavior of the complexes are significantly affected by the nature of the axial pyc^? and H-cpdc^? ligands.     

X-ray photoelectron spectra and structure of polynuclear nickel complexes

Mono- and binuclear nickel complexes of different stoichiometry have been studied by X-ray photoelectron spectroscopy (XPS). The Ni2p, Ni3p, and N1s X-ray photoelectron spectra have been examined, and the role of a ligand in their formation has been determined. As distinct from a low-spin Ni(II) complex, the Ni2p spectra of high-spin Ni(II) compounds show strong satellite lines. For high-spin Ni(II) complexes, which have unpaired 3d electrons, the Ni2p _1/2-Ni2p _3/2 spin-orbit splitting is larger than that for a low-spin Ni(II) compound. The presence or absence of the satellite structure has made it possible to classify these complexes with regard to their magnetic properties. The difference between the Ni2p _3/2 and N1s binding energies has made it possible to estimate the covalence of the metal-ligand bond. The XPS results are consistent with X-ray crystallography data.     

5,15-dialkyl-substituted tetrabenzoporphyrins and their zinc complexes. Synthesis and spectral properties

Reactions of phthalimide with capric and stearic acids gave 1-[1-(1-oxo-1H-isoindol-3-yl)nonylidene]-2,3-dihydro-1H-isoindol-3-one and 1-[1-oxo-1H-isoindol-3-yl)heptadecylidene]-2,3-dihydro-1H-isoindol-3-one, respectively. The latter were heated with zinc(II) acetate to obtain zinc complexes of 5,15-dioctyl-and 5,15-dihexadecyltetrabenzoporphyrins. The same complexes were synthesized by reaction of 1-(1-oxo-1H-isoindol-3-ylmethylidene)-2,3-dihydro-1H-isoindol-3-one with capric or stearic acid in the presence of zinc(II) oxide. The corresponding free porphyrin ligands were obtained by treatment of the metal complexes with sulfuric acid.     

Properties of gold electrode modified with dimercaptosuccinic acid and electrochemical behavior of copper histidine complex

A self-assembled monolayer of meso-2,3-dimercaptosuccinic acid was prepared on the surface of gold disc electrode. The modified electrode was characterized using cyclic voltammetry in copper(II) solution and cyclic voltammetry and electrochemical impedance spectroscopy in the presence of potassium hexacyanoferrate( II)/(III) and hexaammineruthenium (II)/(III) chloride. Binding of copper(II) histidine complex (Cu–His) onto the electrode was successfully achieved for a wide range of tested concentrations, as shown with adsorption transfer stripping voltammetry. Electrode response (logΔI_p) was linearly proportional to logc(Cu–His) with correlation coefficient R³² = 0.9839.     

Theoretical Study of Substituent Effect in Aryl Group Migration in (<Emphasis Type="Italic">para</Emphasis>-C<Subscript>6</Subscript>H<Subscript>4</Subscript>X)Mn(CO)5 Complexes

In this study, we report substituent effect on aryl group migration in (para-C₆H₄X)Mn(CO)₅ complexes using mpw1pw91 quantum chemical calculations. These calculations reveal good linear relationships between barrier energy (ΔE), activation energy (ΔH^?), activation free energy (ΔG^?) values and rate constants with Hammett constants of X-substituents. The occupancy values of Mn–CO_cis and Mn–C(O)-(para-C₆H₄X) bonds in reactant, transition state and product were calculated by Natural bond orbital (NBO) method.     

Protolytic properties of <Emphasis Type="Italic">DL</Emphasis>-alanyl-<Emphasis Type="Italic">DL</Emphasis>-methionine and its complexation in aqueous solutions and micellar solutions

Dissociation constants of DL-alanyl-DL-methionine have been determined in water and micellar solutions of surfactants (anionic sodium n-dodecyl sulfate, cationic cetylpyridinium chloride, and nonionic Brij 35). It has been established that CuA⁺ and CuH_–1A complexes are formed in water and micellar solutions of sodium n-dodecyl sulfate, while CuA⁺, CuH_–1A, and Cu_–2A^– complexes are formed in micellar solutions of cetylpyridinium chloride and Brij 35. Stability of the complexes depends on micelle surface charge and degrees of binding of individual chemical forms by a micellar pseudophase.     

Synthesis,characterization, thermal,antimicrobial and antioxidant studies of some transition metal dithiocarbamates

Metal dithiocarbamate complexes of Co(II) [1], Cu(II) [2], Mn(II) [3], Cr(III) [4], and Pd(II) [5] have been synthesized using sodium N-ethyl-N-phenyldithiocarbamate (NaL). The complexes were characterized by elemental analyses, FTIR and UV–vis spectroscopic techniques, magnetic moment, molar conductance and thermal analyses (TGA and DSC). The infrared spectra indicated the coordination of dithiocarbamate through the two sulphur atoms in a symmetrical bidentate fashion. The thermal behavior of these complexes showed that the hydrated complexes lost water molecules in the first step, followed by decomposition of the ligand molecules in the final steps. Mass loss considerations at these final decomposition steps indicate conversion of the complexes to sulphides. The antimicrobial potentials of the complexes were evaluated against some selected bacteria strains (Escherichia coli, Pseudomonas aureginosa, Salmonella typhi and Staphylococcus aureus) and fungi organisms (Aspergillus flavus and Fasiparium oxysporium). The compounds showed a broad spectrum of fungicidal and bactericidal activities which exceeds that of the control drugs at a 100 μg/mL concentration. The antioxidant properties of the ligand and its Cu(II) complex were evaluated in vitro using DPPH assay, and the complex was found to exhibit better radical scavenging ability than the free ligand.     

Kinetics and mechanism of the catalytic reaction between ozone and <Emphasis Type="Italic">para</Emphasis>-cresol in acetic anhydride

The kinetics of the liquid-phase catalytic oxidation of para-cresol with an ozone-air mixture in the presence of manganese(II) acetate is reported. In an acetic anhydride medium, para-cresol reacts with ozone as para-cresyl acetate, which is formed at the instant the solution to be oxidized is prepared. Under these conditions, the major oxidation products are para-acetoxybenzyl acetate (63.5%) and para-acetoxybenzylidene diacetate (13.7%). The effect of the managanese(II) acetate concentration on the traction selectivity with respect to the oxidation of the methyl group of the substrate is reported. A mechanism consistent with the experimental data available on this catalytic redox reaction is suggested.     

Syntheses,Structures, and Magnetic Properties of Two Mn(II) Coordination Polymers Based on 4-Fluorocinnamic Acid and 1,10-Phenanthroline

Two Mn(II) coordination polymers, {[Mn₃ (Pfca)₆(Phen)₂] · 2DMF} _n (I) and [Mn(Pfca)₂(Phen)(H₂O)] _n (II) (HPfca = 4-fluorocinnamic acid, Phen = 1,10-phenanthroline), were synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and singlecrystal X-ray diffraction (CIF files CCDC nos. 967513 (I), 1542972 (II)). Complex I crystallizes in the triclinic crystal system, space group Pī with a = 11.0821(11), b = 12.2632(12), c = 15.0288(15) Å, α = 87.3760(10)°, β = 88.4610(10)°, γ = 81.2220(10)°, V = 2016.0(3) Å3, ρ_c = 1.369 g/cm³, M _r = 1662.25, Z = 1, F(000) = 853, μ = 0.543 mm^–1, the final R = 0.0592 and wR = 0.1681 for 15498 observed reflections with I > 2σ(I). Complex II is of monoclinic system, space group P2₁/c with a = 18.0539(19), b = 8.5806(9), c = 18.758(2) Å, β = 116.5700(10)°, V = 2599.0(5) ų, ρ_c = 1.491 g/cm³, M _r = 583.44, Z = 4, F(000) = 1196, μ = 0.567 mm^–1, the final R = 0.0337 and wR = 0.0853 for 18139 observed reflections with I > 2σ(I). Complex I features linear Mn(II)-trinuclear units, which form 1D chain structure through F···F weak interactions, and complex II is 1D polymeric Mn(II)-chains. Antiferromagnetic coupling interactions exist within Mn(II)- carboxylate trinuclear in I (J =–0.40 cm^–1) and Mn(II)-carboxylate chain in II (J =–0.45 cm^–1).     

Complexes of palladium(II) and platinum(II) with 6-<Emphasis Type="Italic">tert</Emphasis>-butyl-2-thiouracil

cis-Dihalogeno complexes of platinum(II) and palladium(II) with 6-tert-butyl-2-thiouracil have been synthesized. The mode of coordination of the ligand to metal ions was established by IR and NMR spectroscopy.     

Synthesis of new 1-(3,4-dimethylphenyl)-1,5-dihydropyrazolo[3,4-<Emphasis Type="Italic">d</Emphasis>]pyrimidin-4-one derivatives

New substituted pyrazolo[3,4-d]pyrimidin-4-ones have been synthesized as a result of a series of transformations including hydrolysis of ethyl 5-amino-1H-pyrazole-4-carboxylates, cyclization of the carboxylic acids thus obtained to pyrazolo[3,4-d][1,3]oxazin-4(1H)-ones, and treatment of the latter with substituted anilines. The final pyrazolo[3,4-d]pyrimidin-4-one derivatives can also be synthesized from 5-(arylamido)-1H-pyrazole-4-carboxylic acids in the presence of a catalytic amount of anhydrous zinc(II) chloride.