The influence of modification of periphery of hydroxo(phthalocyaninato)aluminum(III) and (phthalocyaninato)copper(II) on the structure and stability of the molecules as studied by computer simulation and kinetic experiment

The molecular structures of (phthalocyaninato)copper(II) and hydroxo(phthalocyaninato)-aluminum(III) molecules and their substituted analogs were calculated by PM3 quantum-chemical method. It is found that at halogen-, nitro-, halogen-nitro-, and carboxy-substitution the largest steric distortions are observed in complexes with substituents in the 3 position, and effective positive (copper complex) and negative (aluminum complex) charge on coordinated N₄ at all types of substitution is increased and decreased, respectively. The kinetics of transformation at coordinational center in sulphuric acid was studied and success was demonstrated of the comparative analysis of the results of calculations and data on the influence of functional substitution on the stability of complexes in governing the mechanism and regulation of influence of substituents on the reactivity of metallophthalocyanines.     

Structure and properties of tetrakis[3(4)-chlorophthalocyaninato]copper(II) protonated forms in the isolated state and in the sulfuric acid solutions

Results of the quantum-chemical PM3 and experimental spectrophotometric studies of the stepwise protonation of tetrakis[3(4)-chlorophthalocyaninato]copper(II) are presented. The number, structure, and energy characteristics of consecutively protonated isolated molecules of the substituted complexes have been determined; the stability and electron absorption spectra of the complexes protonated forms in concentrated sulfuric acid solution have been studied. The special effect of substitution with halogen on the electronic structure of the exocyclic nitrogen atoms of (phthalocyaninato)copper(II) has been examined.     

Synthesis of novel alkylamino zinc(II) phthalocyanines

The synthesis of tetramethyl‐tetraphthalimidomethyl‐phthalocyaninato zinc(II) ( 6 ) and tetramethyl‐tetraaminomethyl‐phthalocyaninato zinc(II) ( 7 ) is described.     

Peripheral modification and basicity of (phthalocyaninato)-copper(II) according to the electronic spectroscopy and quantum chemical calculation data

Singly, doubly, and triply protonated forms of tetra- and octacarboxy (phthalocyaninato)copper(II) derivatives were identified and characterized by electronic absorption spectra and PM3 quantum chemical calculations. Molecules of carboxy-substituted phthalocyanine copper(II) complexes have a distorted nonplanar structure with specific charge distribution over meso-nitrogen atoms. Singly, doubly, and triply protonated complexes at the meso-nitrogen atoms and carboxy groups exist as mixtures of isomers, which is reflected in splitting of the Q band in the electronic absorption spectra and reduction of its symmetry. The formation of bifurcated hydrogen bonds O ... H⁺ ... N _meso and O ... H⁺ ... O between the neighboring substituents was revealed.     

Ein- und zweikernige MoII-Phthalocyaninate(2–): Darstellung und Eigenschaften von Bis(cyano)phthalocyaninato(2–)molybdat(II) und Bis(phthalocyaninato(2–)molybdän(II))

Mono- and Dinuclear Mo^II Phthalocyaninates(2–): Syntheses and Properties of Bis(cyano)phthalocyaninato(2–)molybdate(II) and Bis(phthalocyaninato(2–)molybdenum(II)) Blue diamagnetic bis(phthalocyaninato(2–)molybdenum(II)) is synthezied by reduction of oxophthalocyaninato(2–)molybdenum(IV) with boiling triphenylphosphine. The Mo–Mo stretching vibration ist observed in the resonance Raman spectrum at 374 cm^–1. It is chemically inert and dissolves in conc. sulfuric acid without decomposition. It reacts with molten tetra(n-butyl)ammonium cyanide to yield redbrown paramagnetic bis[tetra(n-butyl)ammonium] biscyanophthalocyaninato(2–)molybdate(II) (μ_eff = 3.15 μ_B; S = 1). The complex salt is very instable and demetallizes in solution. In the extraordinary UV-VIS-NIR spectrum an intense trip-triplet transition at 7780 cm^–1 together with a very structured B region between 14000 and 21000 cm^–1 of comparable absorbance is observed.     

Racemic iron(III) and cobalt(III) complexes containing a new pentadentate "helmet" phthalocyaninato ligand

Solvothermal reactions of iron(II) acetate tetrahydrate and cobalt(II) acetate tetrahydrate with 1,2-dicyanobenzene in methanol solution result in the formation of racemic six-coordinate iron(III) and cobalt(III) complexes, respectively, with a new bicyclic pentadentate 14,28-[1,3-diiminoisoindolinato]phthalocyaninato ligand.     

Darstellung und Eigenschaften von (Acido)(pyridin)phthalocyaninato(2–)ruthenaten(II); Kristallstruktur von Tetra(n-butyl)ammonium(cyano)(pyridin)phthalocyaninato(2–)ruthenat(II)

Syntheses and Properties of (Acido)(pyridine)phthalocyaninato(2–)ruthenates(II); Crystal Structure of Tetra(n-butyl)ammonium (Cyano)(pyridine)phthalocyaninato(2–)ruthenate(II) Bis(tetra(n-butyl)ammonium bis(acido)phthalocyaninato(2–)ruthenate(II) reacts in boiling pyridine to yield blue purple, diamagnetic tetra(n-butyl)ammonium (acido)(pyridine)phthalocyaninato(2–)ruthenate(II), (ⁿBu₄N)[Ru(X)(py)pc^2–] (X = CN, N₃, NCS, NCO, NO₂). (ⁿBu₄N)[Ru(CN)(py)pc^2–] crystallizes in the orthorhombic space group Pca2₁ (no. 29) with cell parameters a = 28.319(5) Å, b = 29.850(3) Å, c = 24.566(7) Å, Z = 16, with four crystallographically independent complex anions present in the unit cell. Each Ru atom is located outside the centre (Ct) of the corresponding (N_iso)₄ plane (N_iso: isoindoline N atom) and coordinates axially pyridine and cyanide in a mutual trans position. The largest vertical displacement of the Ru atom from the (N_iso)₄ plane towards cyanide (d(Ru–Ct)) is 0.020 Å. The Ru–N_iso distance varies from 1.947(2) to 1.992(2) Å. The average Ru–C and Ru–N_py distance is 2.00 Å and 2.19 Å, respectively. The pc^2– ligand ist slightly distorted towards the cyanide. The cyclic and differential pulse voltammograms of (ⁿBu₄N)[Ru(X)(py)pc^2–] exhibit the first quasi-reversible one electron process (in V) at 0.46 (X = CN), 0.34 (N₃), 0.40 (NCO), 0.47 (NO₂), 0.50 V (NCS) and the second, independent of X, at approximately 1.05 V. The first process is metal directed, the second ring directed. The electronic absorption spectra and the vibrational spectra of (ⁿBu₄N)[Ru(X)(py)pc^2–] are discussed.     

Novel seven coordination geometry of Sn(IV): crystal structures of phthalocyaninato bis(undecylcarboxylato)Sn(IV), its Si(IV) analogue, and phthalocyaninato bis(chloro)silicon(IV). The electrochemistry of the Si(IV) analogue and related compounds

Three newly elucidated crystal structures of group IV phthalocyaninato complexes are reported, along with data for two further SiPc carboxylate complexes. In one of these crystal structures, bis(undecylcarboxylate)Sn(IV) phthalocyanine, the tin ion is seven coordinate, which is a unique finding for this atom in phthalocyanine ring coordination. Comparison of these structures with other group IV phthalocyaninato and related structures reveals differences, illustrating features significant in the chemistries of Si(IV) and Sn(IV) ions. These differences are thought to originate from their differing sizes and polarizabilities. The structures show that the Sn(IV) ion can only occupy an in-plane location in the phthalocyaninato ring where it elongates toward the two axial ligands. When the axial ligands do not facilitate this elongation cis coordination is preferred and the Sn(IV) ion sits above the phthalocyaninato ring plane. In contrast, the Si(IV) structures, with smaller, harder (i.e., less polarizable) Si(IV) ions, are six coordinate with the Si(IV) ion in the phthalocyaninato ring plane in a distorted octahedral symmetry. The electronic spectra and cyclic voltammetry of some of the Si compounds indicate that on the electrode the oxidized/reduced species behave as though they are in a solid film, rather than a soluble freely diffusing species.     

Novel phthalocyanines with naphthalenic substituents

Phthalocyanines with four naphthyl-malonic ester groups on the periphery were synthesized by cyclotetramerization of 4-(1,1-dicarbethoxy-2-(1-naphthyl)-ethyl)-phthalonitrile. The new compounds were characterized by spectroscopic methods. The electronic spectra exhibit intense π–π* transitions from the naphthyl moiety together with the characteristic Q and B bands of the phthalocyanine core. The electrochemical properties of the 2,9,17,23-tetra-(1,1-(dicarbethoxy)-2-(1-naphthyl)-ethyl) phthalocyaninato copper(II) complex were studied by cyclic voltammetry.     

Darstellung,Eigenschaften und Kristallstruktur von Bis(phthalocyaninato)cer(IV)

Preparation, Properties and Crystal Structure of Bis(phthalocyaninato)cerium(IV) The anodic or chemical oxidation with dibenzoylperoxide of solutions of bis(phthalocyaninato)cerate(III) in dichloromethane yields selectively sparely soluble bis(phthalocyaninato)cerium(IV), [Ce(Pc(2-)) 2 ]. Green, monoclinic needles cristallize with a = 18.783(12) Å b = 18.739(16) Å c= 15.618(10) Å ß114.30(7)°; Z = 4; space group C2/c. [Ce(Pc(2–)) 2 ] is a sandwich complex in which the cerium Atom is eightfold coordinated by the isoindole nitrogens of the two staggered convex Pc-rings. The u.v.-vis., m.i.r., f.i.r. and resonance Raman spectra are consistent with the structure.     

Sandwich-type tetrakis(phthalocyaninato) dysprosium-cadmium quadruple-decker SMM

Homoleptic tetrakis[2,3,9,10,16,17,23,24-octa(butyloxy)phthalocyaninato] dysprosium-cadmium quadruple-decker complex 1 was isolated in relatively good yield of 43% from a simple one-pot reaction. This compound represents the first sandwich-type tetrakis(phthalocyaninato) rare earth-cadmium quadruple-decker SMM that has been structurally characterized.     

Application of zone-melting technique to metal chelate systems-X Zone-refining of bis(acetylacetonato)beryllium(II), tris(acetylacetonato)aluminium(III) and bis(di-isovalerylmethanato)copper(II)

Bis(acetylacetonato)beryllium(II), tris(acetylacetonato)aluminium(III) and bis(di-isovaleryl-methanato)copper(II) were zone-refined. Also crude beryllium(II), aluminium(III) and copper(II) salts were purified by zone-melting the above-mentioned chelates, obtained by precipitation from aqueous methanol solutions. Some contaminants were excluded at the stage of chelate formation and the remainder were concentrated at the terminal end of a zone-refining column.     

M(mu-CN)Fe(mu-CN)M' chains with phthalocyanine iron centers: preparation, structures, and isomerization

The molecular building blocks Fe(II)Pc (Pc = phthalocyaninato2-), Fe(III)Pc, ZnPc, Cp(dppe)Fe, and Cp(PPh3)2Ru were combined in the cyanide-bridged dinuclear reference compounds with M-CN-ZnPc and M-CN-FePc-CN arrays containing Fe(II)Pc and Fe(III)Pc. The linear trinuclear species with the M(mu-CN)Fe(mu-CN)M' backbone were prepared for both Fe(II)Pc and Fe(III)Pc centers, for terminal Fe/Fe, Fe/Ru, and Ru/Ru combinations and for all three possible cyanide orientations (M-CN-Fe-NC-M', M-CN-Fe-CN-M', and M-NC-Fe-CN-M'). The 15 complexes obtained were identified from their IR spectra and six structure determinations. The preferred orientation of the cyanide bridges could be established starting from the [Fe-NC-Fe(III)Pc-CN-Fe]+ complex, which is labile in solution and isomerizes to the corresponding [Fe-CN-Fe(III)Pc-NC-Fe]+ complex. A kinetic analysis of this isomerization has yielded an activation barrier of roughly 110 kJ/mol.     

Simultaneous sorption of nonionic surfactant (alkylmonoethers) and copper(II) in a weak acid polyacrylic cation exchanger

The mutual influence of copper(II) cations and nonionic surfactant alkylmonoethers on their simultaneous sorption by the hydrogen form of Purolite C 106 polyacrylic acid functionalized cation exchanger was investigated considering the suitability for the prevention of environmental contamination. Sorption isotherms were measured and sorption equilibrium coefficients calculated. The modelling of copper(II) sorption and copper(II) carboxyl complex formation was carried out. The sorption of copper(II) proceeds predominantly by complex (ionic and coordinate) bonding followed by the change in pH, also by single coordinate bonding. The mutual action of copper(II) and alkylmonoethers leads to a decrease in the equilibrium sorption for both copper(II) and the surfactant. The sorption of copper(II) and alkylmonoethers could be applicable for the purification of sewage including copper plating rinsewater from both contaminants simultaneously for the control of copper(II) and the surfactant in sewage effluents. Received: 15 May 2000 Accepted: 9 May 2001     

E.p.r. spectra of mixed valence copper(II)-copper(I) systems

Summary Mixed valence (thiosemicarbazone)₂Cu^II-Cu^I complexes were prepared and their e.p.r. spectra in the polycrystalline state studied. Complexes derived from acetophenone- and propiophenonethiosemicarbazones exhibit strong copper(II)-copper(II) and copper(II)-copper(I) interactions, whereas those derived from benzyl methyl ketone and cyclohexanone show strong copper(II)-copper(I) interaction but almost no copper(II)-copper(II) interaction.     

Synthesis and characterization of iron(III), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes of salicylidene-N-anilinoacetohydrazone (H2L1) and 2-hydroxy-1-naphthylidene-N-anilinoacetohydrazone (H2L2)

Salicylidene-N-anilinoacetohydrazone (H(2)L(1)) and 2-hydroxy-1-naphthylidene-N-anilinoacetohydrazone (H(2)L(2)) and their iron(III), manganese(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes have been synthesized and characterized by IR, electronic spectra, molar conductivities, magnetic susceptibilities and ESR. Mononuclear complexes are formed with molar ratios of 1:1, 1:2 and 1:3 (M:L). The IR studies reveal various modes of chelation. The electronic absorption spectra and magnetic susceptibility measurements show that the iron(III), nickel(II) and cobalt(II) complexes of H(2)L(1) have octahedral geometry. While the cobalt(II) complexes of H(2)L(2) were separated as tetrahedral structure. The copper(II) complexes have square planar stereochemistry. The ESR parameters of the copper(II) complexes at room temperature were calculated. The g values for copper(II) complexes proved that the Cu-O and Cu-N bonds are of high covalency.     

Preparation and study of bis(theophyllinato) copper(II) compounds

Bis(theophyllinato) copper(II) dihydrate and its anhydrous form, were prepared. Their thermal, spectral and magnetic behaviours were investigated. Magnetic susceptibility studies show that the dihydrate form can be fitted to the Curie law. The magnetic behaviour of the anhydrous form is interpreted in terms of antiferromangetically exchange-coupled pairs of copper atoms. The change in magnetic properties as the dihydrate is dehydrated implies that structural rearrangement in first coordination sphere of copper accompanies the dehydration process. For bis(theophyllinato)copper(II) dihydrate we propose a pseudo octahedral coordination of copper(II) in a polymeric chain, and for the anhydrous form four-coordination in binuclear units.     

Synthesis,characterization and catalytic activity of peripherally tetra‐substituted Co(II) phthalocyanines for cyclohexene oxidation

New 3,3‐diphenylpropoxyphthalonitrile (5) was obtained from 3,3‐diphenylpropanol (3) and 4‐nitrophthalonitrile (4) with K₂CO₃ in DMF at 50 °C. The novel cobalt(II) phthalocyanine complexes, tetrakis‐[2‐(1,4‐dioxa‐8‐azaspiro[4.5]dec‐8‐yl)ethoxy] phthalocyaninato cobalt(II) (2) and tetrakis‐(3,3‐diphenylpropoxy)phthalocyaninato cobalt(II) (6) were prepared by the reaction of the phthalonitrile derivatives 1 and 5 with CoCl₂ by microwave irradiation in 2‐(dimethylamino)ethanol for at 175 °C, 350 W for 7 and 10 min, respectively. These new cobalt(II)phthalocyanine complexes were characterized by spectroscopic methods (IR, UV–visible and mass spectroscopy) as well as elemental analysis. Complexes 2 and 6 are employed as catalyst for the oxidation of cyclohexene using tert‐butyl hydroperoxide (TBHP), m‐chloroperoxybenzoic acid (m‐CPBA), aerobic oxygen and hydrogen peroxide (H₂O₂) as oxidant. It is observed that both complexes can selectively oxidize cyclohexene to give 2‐cyclohexene‐1‐ol as major product, and 2‐cyclohexen‐1‐one and cyclohexene oxide as minor products. TBHP was found to be the best oxidant since minimal destruction of the catalyst, higher selectivity and conversion were observed in the products. Copyright © 2012 John Wiley & Sons, Ltd.     

Extraction of lead(II) and copper(II) from salicylate media by tributylphosphine oxide.

Tributylphosphine oxide (TBPO) is proposed as an extractant for the extraction of lead(II) and copper(II) from salicylate media. The optimum conditions were evaluated by varying the experimental parameters, such as the pH, sodium salicylate concentration, tributylphosphine oxide (TBPO) concentration, shaking period and various diluents. The probable extracted species, deduced from log-log plots were Pb(HSal)2.2TBPO and Cu(HSal)2.2TBPO. The extraction took place through a solvation mechanism. The method permits the binary separation of lead(II) and copper(II) from commonly associated elements as well as the mutual separation of lead(II) and copper(II). The method is applicable to the determination of lead(II) and copper(II) in various alloys as well as environmental and pharmaceutical samples.     

Specificity of complex formation of benzoin (phthalazin-1-yl)hydrazone with copper(II) and nickel(II): Physicochemical study and quantum-chemical simulation

Benzoin (phthalazin-1-yl)hydrazone and its complexes with copper(I), copper(II), and nickel(II) were synthesized. Acid-base properties of benzoin (phthalazin-1-yl)hydrazone were studied, and its ionization constants and energies of possible conformers were calculated by quantum-chemical methods. The structure of the isolated complexes was determined on the basis of their elemental compositions, IR spectra, and data of thermogravimetric, conductometric, and magnetochemical measurements. Copper(II) acetate with benzoin (phthalazin-1-yl)hydrazone forms dinuclear complex, nickel(II) acetate and chloride produce mononuclear octahedral complexes, and copper(II) halides give rise to copper(I) complexes with the oxidized hydrazone.