Anthracene Substituted Co (II) and Cu (II) phthalocyanines; Preparations,Investigation of Catalytical and Electrochemical Behaviors

An approach to investigation of catalytical behaviors of Co (II) and Cu (II) phthalocyanines is reported that is based on changing any parameter to effect these behaviors. Towards this end, new anthracene substituted Co (II) and Cu (II) phthalocyanines were prepared and characterized spectroscopic methods. New cobalt (II) and copper (II) phthalocyanines were used as catalyst for oxidation of different phenolic compounds (such as 2,3‐dichlorophenol, 4‐methoxyphenol, 4‐nitrophenol, 2,3,6‐trimethylphenol) with different oxidants. Then, electrochemical characterization of cobalt (II) and copper (II) phthallocyanines were determined by using cyclic voltammetry (CV) and square wave voltammetry (SWV) techniques. Although copper (II) phthalocyanine showed similar Pc based electron transfer processes, cobalt (II) phthalocyanine showed metal and ligand based reduction reactions as expected.     

Liquid-phase catalytic oxidation of organic substrates by a recyclable polymer-supported copper(II) complex

Chloromethylated polystyrene beads cross-linked with 6.5 % divinylbenzene were functionalized with 2-(2′-pyridyl) benzimidazole (PBIMH) and on subsequent treatment with Cu(OAc)₂ in methanol gave a polymer-supported diacetatobis(2-pyridylbenzimidazole)copper(II) complex [PS-(PBIM)₂Cu(II)], which was characterized by physicochemical techniques. The supported complex showed excellent catalytic activity toward the oxidation of industrially important organic compounds such as phenol, benzyl alcohol, cyclohexanol, styrene, and ethylbenzene. An effective catalytic protocol was developed by varying reaction parameters such as the catalyst and substrate concentrations, reaction time, temperature, and substrate-to-oxidant ratio to obtain maximum selectivity with high yields of products. Possible reaction mechanisms were worked out. The catalyst could be recycled five times without any metal leaching or much loss in activity. This catalyst is truly heterogeneous and allows for easy work up, as well as recyclability and excellent product yields under mild conditions.     

1D Azido bridged Cu(II) coordination polymer with 1,3-oxazolidine ligand as an effective catalyst for green click synthesis of 1,2,3-triazoles

A new 1D azido bridged Cu(II) coordination polymer with 1,3-oxazolidine based ligand, [Cu(H₃L)(μ_1,3-N₃)(N₃)]_n ( 1 ), was synthesized and characterized by elemental analysis and spectroscopic methods. The structure of 1 was also determined by single crystal X-ray analysis which indicated the 1D polymeric chain is generated by end-to-end (EE) azide bridge. The obtained compound was employed as catalyst in green click synthesis of β-hydroxy-1,2,3-triazoles from one-pot three-component cycloaddition reaction of epoxide-azide-alkyne. The catalytic reactions were carried out in water as a safe, cheap and green solvent. The catalytic studies indicated that the obtained 1D azido bridged Cu(II) coordination polymer is an active catalyst for preparing β-hydroxy-1,2,3-triazoles. The effect of temperature on the selectivity of the catalytic system was studied and the results indicated this catalytic system has high selectivity at low temperatures. The structure the product obtained from the reaction of 2,3-epoxypropylphenylether, azide and 1-ethynyl-1-cyclohexanol ( T4 ) was determined by single crystal X-ray analysis. The results indicate Cu(II) coordination polymers can be a new class of catalytic systems for green click synthesis of 1,2,3-triazoles.     

Synthesis of 5,6-O-Cyclohexylidene-1-amino-3-azahexane and Its Co(II), Ni(II), Cu(II) Complexes

5,6-O-Cyclohexylidene-1-amino-3-azahexane (L) is synthesized from 1-chloro-2,3-O-cyclohexylidenepropane, which is prepared by the reaction between epichlorohydrin and cyclohexanone. In this reaction, BF₃ · OEt₂ is used as a catalyst. Complexes of Co(II), Ni(II) and Cu(II) acetates with this ligand are prepared. The structures of the ligand and its complexes are proposed based on elemental analysis, IR and UV-VIS spectroscopy, magnetic susceptibility, conductometry, and ¹H and ¹³C NMR spectroscopy.     

Spectral and Thermal Studies of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) Complexes with 3-methylglutaric Acid

Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) 3-methylglutarates were prepared as solids with general formula MC₆ H₈ O₄ ×n H₂ O, where n =0–8. Their solubilities in water at 293 K were determined (7.0×10⁻² −4.2×10⁻³ mol dm⁻³ ). The IR spectra were recorded and thermal decomposition in air was investigated. The IR spectra suggest that the carboxylate groups are mono- or bidentate. During heating the hydrated complexes lose some water molecules in one (Mn, Co, Ni, Cu) or two steps (Cd) and then mono- (Cu) or dihydrates (Mn, Co, Ni) decompose to oxides directly (Mn, Cu, Co) or with intermediate formation of free metals (Co, Ni). Anhydrous Zn(II) complex decomposes directly to the oxide ZnO. This revised version was published online in July 2006 with corrections to the Cover Date.     

Cobalt(II) porphyrazine catalysed reduction of nitrite

Studies on the catalytic reduction of nitrite on carbon electrodes modified with Co(II) tetra-2,3-pyridinoporphyrazine (CoTppa, 1), N,N′,N′′,N′′′-tetramethyltetra-2,3-pyridinoporphyrazine ([CoTm-2,3-tppa]⁴⁺, 2) and Co(II) N,N′,N′′,N′′′-tetramethyltetra-3,4-pyridinoporphyrazine ([CoTm-3,4-tppa]⁴⁺, 3) are reported. There is a close correspondence between the proximity of the methyl groups to the porphyrazine ring and the catalytic activity of the porphyrazine complexes. Bulk electrolysis gave ammonia and hydroxylamine as some of the products. The catalytic activity of the cationic complex, 3, towards the detection of low concentrations of nitrite (<10⁻⁹ M) in water containing sodium sulfate, was compared with the activities of the anionic cobalt(II) tetrasulfophthalocyanine ([CoTSPc]⁴⁻, 4) and the mixed [Co^IITm-3,4-tppa]⁴⁺·[CoTSPc]⁴⁻ (5) complexes. Complex 5 showed the best catalytic activity of the three in that large currents were obtained for very low concentrations of nitrite.     

Spectrothermal studies of 1,10-phenanthroline complexes of Co(II), NI(II), Cu(II) and Cd(II) orotates

The 1,10-phenanthroline (phen) complexes of Co(II), Ni(II), Cu(II) and Cd(II) orotates were synthesized and characterized by elemental analysis, magnetic susceptibility, spectral methods (UV-vis and FTIR) and thermal analysis techniques (TG, DTG and DTA). The Co(II), Ni(II), Cu(II) and Cd(II) ions in diaquabis(1,10-phenanthroline)metal(II) diorotate octahedral complexes [M(H₂O)₂(phen)₂](H₂Or)₂·nH₂O (M=Co(II), n=2.25; Ni(II), n=3; Cu(II) and Cd(II), n=2) are coordinated by two aqua ligands and two moles of phen molecules as chelating ligands through their two nitrogen atoms. The monoanionic orotate behaves as a counter ion in the complexes. On the basis of the first DTG_max, the thermal stability of the hydrated complexes follows the order: Cd(II), 68°C 68°C     

New Complexes of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with 3,3-dimethylglutaric Acid

Conditions for the preparation of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II)3,3-dimethylglutarates were investigated and their quantitative composition, solubility in water at 293 K and magnetic moments were determined. IR spectra and powder diffraction patterns of the complexes prepared with general formula MC₇H₁₀O₄⋅nH₂O (n=0−2) were recorded and their thermal decomposition in air were studied. During heating the hydrated complexes of Mn(II),Co(II), Ni(II) and Cu(II) are dehydrated in one step and next all the anhydrous complexes decompose to oxides directly (Mn, Co, Zn) or with intermediate formation free metal (Ni,Cu) or oxocarbonates (Cd). The carboxylate groups in the complexes studied are bidentate. The magnetic moments for the paramagnetic complexes of Mn(II), Co(II), Ni(II) and Cu(II)attain values 5.62, 5.25, 2.91 and 1.41 M.B., respectively. This revised version was published online in August 2006 with corrections to the Cover Date.     

Spectral,thermal and magnetic investigations of Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) 4-methylphthalates

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)₂]·nH₂o (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.     

Studies of Mn(II), Co(II), Ni(II) and Cu(II) Chelates with 3-phenyl-4-(p-methoxy- phenylazo)-5-pyrazolone

Mn(II), Co(II), Ni(II) and Cu(II) chelates with3-phenyl-4-(p-methoxyphenylazo)-5-pyrazolone have been synthesized and were characterized by elemental and thermal analyses as well as by IR, UV-VIS, ¹HNMR, conductometric and magnetic measurements. The first stage in the thermal decomposition process of these complexes shows the presence of water of hydration, the second denotes the removal of the coordinated water molecules. The final decomposition products were found to be the respective metal oxides. The data of the investigated complexes suggest octahedral geometry with respect to Co(II) 1:1, tetrahedral for Ni(II) 1:1and 2:3; square planar for Cu(II) 1:1 and 2:3; the complexes with no coordinated water molecules (2:3) Co(II) and Mn(II) complexes are tetrahedral. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis of non-peripherally substituted tetra(dihexylmalonate) alcohol soluble phthalocyanines

Dimethyl-(2,3-dicyanophenyl)malonate was prepared by the reaction of dimethylmalonate and 3-nitrophthalonitrile. A cyclotetramerization reaction of dimethyl-(2,3-dicyanophenyl)malonate with the corresponding divalent metal salt was achieved in hexanol in the presence of DBU, affording the non-peripherally substituted tetra(dihexylmalonate) Cu(II), Pd(II), and Co(II) phthalocyanines. Transesterification occurred under these reaction conditions, so that methyls in the phthalonitrile derivative were converted into hexyl groups during phthalocyanine formation in hexanol. The new compounds were characterized by elemental analyses, FT-IR, ¹H-NMR, ¹³C-NMR, UV-Vis, and mass spectral data.     

Schiff-Basen aus 1,3-Dicarbonylverbindungen und Triaminen und ihre Fe (III)-, Co (III)-, Ni(II)- und Cu(II)-Komplexe

Schiff bases of 1,3-dicarbonyl compounds with triamines and their Fe(III), Co(III), Ni(II) and Cu(II) complexes The preparation of new hexadentate ligands obtained by the reaction of cis, cis-1,3,5-triaminocyclohexane (tach) or 1,1,1-tris (aminomethyl)ethane (tame) with an 2-ethoxymethylidene-1,3-dicarbonyl compound as well as their Fe(III), Co(III), Ni(II) and Cu(II) complexes is reported. Fe(III) and Co(III) yield neutral complexes with an octahedral N₃O₃-coordination sphere, Ni(II) and Cu(II) complexes with a square-planar coordination-sphere. In the later complexes one of the bidentate branches of the ligand is not deprotonated and stays uncoordinated.     

Single‐step oxidative homocoupling of aryl Grignard reagents via Co(II), Ni(II) and Cu(II) Complexes under air

A simple catalytic system of direct synthesis for the symmetrical biaryls using catalytic amounts of Co(II), Ni(II) and Cu(II) complexes has been developed. The reaction system involves in situ synthesis of Grignard reagents. The complexes, containing bidentate Schiff base and dmit (2‐thioxo‐1,3‐dithiole‐4,5‐dithiolate) ligands, were compatible with diverse functionalities and afford a high yield of biaryls in a single step, proving to be promising catalysts in homocoupling reactions. Atmospheric oxygen is used as an oxidant which renders a green, simple and economical catalytic route. Copyright © 2014 John Wiley & Sons, Ltd.     

Syntheses and spectrothermal studies of triethanolamine complexes of Co(II), Ni(II), Cu(II) and Cd(II) squarates

The triethanolamine complexes, [M(tea)₂]sq·nH₂O, (n=2 for Co(II), n=0 for Ni(II), Cu(II) and n=1 for Cd(II), tea=triethanolamine, sq²⁻=squarate), have been synthesized and characterized by elemental analyses, magnetic susceptibility and conductivity measurements, UV-Vis and IR spectra, and thermal analyses techniques (TG, DTG and DTA). The Co(II), Ni(II) and Cu(II) complexes possess octahedral geometry, while the Cd(II) complex is monocapped trigonal prismatic geometry. Dianionic squarate behaves as a counter ion in the complexes. The thermal decomposition of these complexes takes place in three stages: (i) dehydration, (ii) release of the tea ligands and (iii) burning of organic residue. On the basis of the first DTG_max of the decomposition, the thermal stability of the anhydrous complexes follows the order: Ni(II), 289°C>Co(II), 230°C>Cu(II), 226°C>Cu(II), 170°C in static air atmosphere. The final decomposition products — the respective metal oxides — were identified by FTIR spectroscopy.     

Synthesis and electrochemical properties of a series of novel tetra(4-benzoyl)phenoxyphthalocyanine derivatives

A novel phthalocyanine,2,9(10),16(17),23(24)-tetra(4-benzoyl)phenoxyphthalocyanine,and its complexes with Zn(II),Cu(II),Co(II),and Ni(II) have been synthesized and characterized by a combination of elemental analysis,IR,1 H NMR,UV-vis spectroscopy and mass spectrometry.All of the materials are very soluble in common organic solvents such as dichloromethane,chloroform,tetrahydrofuran,N,N-dimethylformamide and dimethyl sulfoxide.The Q band wavelengths of the complexes decrease in the order:Zn > Cu > Ni > Co.Redox processes were observed at 1.06,0.74,0.51 and 0.98 V for the free phthalocyanine,at 0.72 and 1.04 V for the Co(II) complex,at 1.24,0.77,0.24,0.61 and 0.91 V for the Cu(II) complex,and at 0.74 and 1.20 V for the Ni(II) complex.The cyclic voltammograms of the phthalocyanine ring of the four species are similar,with reduction and oxidation couples each involving a one-electron transfer process.     

Efficient and reusable Cu (II)-metalated silica-based inorganic-organic hybrid catalyst for dye degradation

An efficient silica-based inorganic-organic hybrid was synthesized by using 3-(2-aminoethylamino)propyltrimethoxylsilane as linker and 2-Quinolinecarboxaldehyde for Schiff's base formation which was further coordinated by Cu (II) chloride. The hybrid was characterized by relevant techniques, i.e., FT-IR, DRUV-Vis, SEM, EDX, ICP-AES, TGA and EPR technique which support its formation. The synthesized hybrid material was successfully used as heterogeneous catalyst for degrading Reactive Black-5 (RB-5), a non-biodegradable diazo dye. The degradation mechanism follows advanced oxidation technique utilizing hydrogen peroxide as an environmentally amiable green oxidant; where the hybrid catalyst decomposes H₂O₂ to generate ·OH free radicals. Effects of dye concentration, H₂O₂ concentration and temperature variation on dye degradation process were studied and best reaction conditions for maximum degradation of RB-5 were also worked out. The catalyst showed 87% dye degradation in 130 ?min at best reaction conditions. Easy separation, reusability and efficient dye degradation ability of the catalyst are the motivating factors for the development of such hybrid material for solving critical environmental issues.     

Studies on Binuclear Co(II) and Cu(II) Complexes of Tridentate N-(2-Carboxyphenyl)Salicylideneimine

Homo Cu(II) and Co(II) binuclear complexes H[MLClMCl₂] formed by using the donor properties of the cis two oxygen atoms of the tridentate N-(2-carboxyphenyl)-salicylaldimine Schiff base derived from salicylaldehyde and anthranilic acid have been synthesized. It was found that the Cu(II) “complexed ligand” readily reacts with CoCl₂ to form mononuclear Co(II) and binuclear oxygen bridged Co(II) complex [Co₂-L₂](H₂O)₂. The structure of the so prepared complexes was investigated using microchemical analysis, molar conductance measurements as well as electronic and vibrational spectral studies. It was concluded that in the Cu(II) binuclear complex, the Cu(II) ion inside the “complexed ligand” has a planar structure while the other Cu(II) ion is distorted away from planarity. In the Co(II) binuclear complex, the Co atom of the “complexed ligand” is distorted from tetrahedral structure when it coordinates to the second Co atom.     

Co(II), Ni(II) and Cu(II) Complexes with 1-(4-Hydroxyphenyl)-1H-1,2,4-Triazole

New complexes of Co(II), Ni(II), and Cu(II) with 1-(4-hydroxyphenyl)-1H-1,2,4-triazole (L) of the composition ML₂(H₂O)₂(NO₃)₂ · nH₂O (M = Co(II), n = 3; M = Ni(II), n = 0; M = Cu(II), n = 0) were synthesized and studied by photoelectron and IR spectroscopy, magnetochemistry, thermogravimetry, and X-ray powder diffraction analysis. The type of _eff(T) relationship suggests that paramagnetic centers in the Co(II) chloride and Cu(II) nitrate and bromide complexes are involved in antiferromagnetic exchange interactions. The exchange energy values were estimated by the molecular field method.     

Investigation of mononuclear,dinuclear, and trinuclear transition metal (II) complexes derived from an asymmetric Salamo‐based ligand possessing three different coordination modes

A new asymmetric Salamo‐based ligand H₂L was synthesized using 3‐tert‐butyl‐salicylaldehyde and 6‐methoxy‐2‐[O‐(1‐ethyloxyamide)]‐oxime‐1‐phenol. By adjusting the ratio of the ligand H₂L and Cu (II), Co (II), and Ni (II) ions, mononuclear, dinuclear, and trinuclear transition metal (II) complexes, [Cu(L)], [{Co(L)}₂], and [{Ni(L)(CH₃COO)(CH₃CH₂OH)}₂Ni] with the ligand H₂L possessing completely different coordination modes were obtained, respectively. The optical spectra of ligand H₂L and its Cu (II), Co (II) and Ni (II) complexes were investigated. The Cu (II) complex is a mononuclear structure, and the Cu (II) atom is tetracoordinated to form a planar quadrilateral structure. The Co (II) complex is dinuclear, and the two Co (II) atoms are pentacoordinated and have coordination geometries of distorted triangular bipyramid. The Ni (II) complex is a trinuclear structure, and the terminal and central Ni (II) atoms are all hexacoordinated, forming distorted octahedral geometries. Furthermore, optical properties including UV–Vis, IR, and fluorescence of the Cu (II), Co (II), and Ni (II) complexes were investigated. Finally, the antibacterial activities of the Cu (II), Co (II), and Ni (II) complexes were explored. According to the experimental results, the inhibitory effect was found to be enhanced with increasing concentrations of the Cu (II), Co (II), and Ni (II) complexes.     

Synthesis and spectral studies of pyranone derivative and its Cu(II), Co(II), Ni(II) and Zn(II) complexes

Under the thermolysis condition, 5-phenyl-2,3-dihydro-2,3-furandione (IV) in inert aprotic solvents as p-xylene at 130–140°C yields 3-benzoyl-4-hydroxy-6-phenyl-2H-pyran-2-one (VI) via phenyl ketene (V). The compound (VI) was converted into the corresponding 3-benzoyl-4-hydroxy-6-phenylpyridin-2(1H)-one (VII), and 3-benzoyl-2-oxo-6-phenyl-2H-pyran-4-yl acetate (VIII), by its reactions with ammonium hydroxyde, and acetic anhydride, respectively. On the other hand, a series of new various metal complexes (IX-XIa, XIb) of VI was synthesized. The results suggest that the compound VI as bidentate ligand indicate a binuclear structure for the Cu(II) complex with square-planar geometry. The Ni(II) and Zn(II) complexes are of tetrahedral and the Co(II) complex is also octahedral geometry with water molecules at the axial positions. The structures of compounds and complexes were characterized on the basis of elemental analysis, Mass, IR, ¹H, and ¹³C NMR spectra. The text was submitted by the authors in English.