Thermal decomposition kinetics of Schiff base complexes of copper(II) and palladium(II)

Thermogravimetric (TG), derivative thermogravimetric (DTG) and differential thermal analysis (DTA) curves of CuL₂ and Pd(LH)₂Cl₂ (LH=salicylidene-2-aminofluorene and 2-hydroxy-1-naphthalidene-2-aminofluorene) in air are studied. Mass loss considerations at the main decomposition stages indicate conversion of the complex to oxides. Mathematical analysis of TG data shows that first order kinetics are applicable in all cases. Kinetic parameters (energy and entropy of activation and preexponential factor) are reported.     

New complexes of iron(III), cobalt(II), nickel(II) and copper(II) with Schiff bases derived from 2-aminocyclopent-1-ene-1-dithiocarboxylic acid

Summary Fe^III, Co^II, Ni^II and Cu^II, complexes of a new Schiff base ligand, prepared by condensing 2-aminocyclopent-1-ene-1-dithiocarboxylic acid with benzaldehyde (ACB), and also Cu^II and Ni^II complexes of a second Schiff base ligand prepared by condensing 2-aminocyclopent-1-ene-1-dithiocarboxylic acid with salicylaldehyde (ACS), have been prepared and characterized by elemental analyses, conductivity measurements, magnetic and spectral (electronic, i.r. and e.p.r.) studies. The i.r. spectra suggest that both ACB and ACS are acting as bidentate ligands, coordinating through one of the sulphur atoms and through the azomethine nitrogen atom. The magnetic moment of the Fe^III complex indicates spin crossover behaviour. Square planar structures have been assigned to the Cu^II and Ni^II complexes and a tetrahedral structure to the Co^II complex. The e.p.r. spectra of the Cu^II complexes suggest a square planar environment with rhombic distortion around the Cu^II ion.     

Synthesis,characterization and antifungal activities of copper(II), zinc(II), cobalt(II) and nickel(II) complexes with the Schiff base derived from 3-chlorobenzaldehyde and glycine

Summary The Schiff base (1) derived from 3-chlorobenzaldehyde and glycine, and its copper(II), zinc(II), cobalt(II) and nickel(II) complexes were prepared and characterized by elemental analyses, conductivity measurements and spectra. The results suggest that (1) acts as a bidentate ligand, bonding to metal ions through imino nitrogen and carboxylate oxygen. It is a 1∶1 electrolyte, but all its complexes (2) are nonelectrolytes. The complexes possess strong inhibition to the fungi Gypseum, floccosum, Canis and Rubrum.     

Thermal decomposition kinetics of vanillidene anthranilic acid complexes of cobalt(II), nickel(II), copper(II) and zinc(II)

The thermal decomposition of cobalt(II), nickel(II), copper(II) and zinc(II) complexes of the Schiff base vanillidene anthranilic acid was studied by TG. The chelates show somewhat similar TG plots when heated in an atmosphere of air. Thermoanalytical data (TG and DTG) of these chelates are presented in this communication. Interpretation and mathematical analysis of these data and evaluation of order of reaction, the energy and entropy of activation based on the differential method employing the Freeman-Carroll equation, the integral method using Coats-Redfern equation and the approximation method using the Horowitz-Metzger equation are also given. On the basis of experimental findings in the present course of studies, it is concluded that the relative thermal stability of vanillidene anthranilic acid chelates can be aligned as Co(II)Ni(II)>Zn(II)>Cu(II).

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Zusammenfassung Die thermische Zersetzung von Cobalt(II)-, Nickel(II)-, Kupfer(II)- und Zink(II)-Komplexen der Schiffschen Base Vanillidenanthranilsäure wurde thermogravimetrisch untersucht. Die Chelate zeigen in einer Luftatmosphäre ähnliche TG-Kurven. Thermoanalytische Daten (TG and DTG) dieser Chelate werden mitgeteilt, interpretiert und mathematisch analysiert. Ebenfalls werden die Reaktionsordnung und die Energie und Entropie der Aktivierung nach der von Freeman-Carroll angewandten differentiellen Methode, nach der auf der Coats-Redfern-Gleichung basierenden integralen Methode und nach der die Horowitz-Metzger Gleichung benutzenden Näherungsmethode bestimmt. Aus den Befunden wird geschlossen, dass die thermische Stabilität von Vanillidenanthranilsäure-Chelaten in der Reihenfolge Co(II)Ni(II)>Zn(II)> >Cu(II) abnimmt.

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, , . - . . , , - , , - . , Ni>Zn>u.

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We thank Dr. C. P. Savariar, Professor of Chemistry, University of Calicut for encouragement. We are also grateful to the University Grants Commission for the award of a Senior Research Fellowship to one of us (J. C).     

Thermal decomposition kinetics of thiophene-2-carboxaldehyde thiosemicarbazone complexes of nickel(II) and palladium(II)

The thermal analysis of Ni(II) and Pd(II) complexes with thiophene-2-carboxaldehyde thiosemicarbazone have been studied using TG technique. Their decompositions are subjected to critical evaluation using the equations of Coats-Redfern, Horowitz-Metzger and modified Horowitz-Metzger and the kinetic parameters (non-isothermal method) have been evaluated for each step of decomposition by the method of weighted least-squares.     

The stereochemistry of the nickel(II), cobalt(II), copper(II) and palladium(II) complexes of the tetradentate Schiff base derived from salicylaldehyde and isobutylenediamine

The ligand N,N′-bis(salicylidene)-1,1-(dimethyl)ethylenediamine (Sal₂-i-bn) and its complexes with divalent nickel, cobalt, copper and palladium have been synthesized for the first time. The magnetic properties of the complexes have been investigated between 310 and 80°K. The nickel and palladium complexes are diamagnetic. The cobalt complex is low-spin with a magnetic moment of 2·40 → 2·22 B.M. and the copper complex has a temperature independent magnetic moment of 1·81 B.M. Electron paramagnetic resonance spectra of the powders have been measured at room and at liquid air temperatures while the solution spectra of the complexes were studied at room temperature only. The magnetic moment of the copper complex agrees with that calculated from the paramagnetic resonance g₀ ≅ 2·09 at liquid air temperature.The molecular weights were determined by mass spectrometry and by osmometry. Both methods provide evidence for the monomeric nature of the complexes. The i.r., u.v. and visible spectra are very similar to those of other related complexes. The complexes in the solid state and in solution and presumably in the vapor state are square-planar.     

Template synthesis and spectral characterization of some Schiff base complexes derived from quinoxaline-2-carboxaldehyde and L-histidine

New Schiff base complexes of Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) were synthesized by template condensation of quinoxaline-2-carboxaldehyde, L-histidine, and the metal compound, and were characterized by elemental analysis, fourier transform infrared spectroscopy, electronic spectra, conductance measurements, magnetic susceptibility measurements, ESR spectra, and thermal analysis. In all the complexes, the Schiff base coordinates through azomethine nitrogen, quinoxaline nitrogen, and carboxylato oxygen. The physicochemical and spectroscopic measurements reveal square planar geometry for the copper(II) complex, tetrahedral geometry for the manganese(II), cobalt(II), and zinc(II) complexes, and octahedral geometry for the iron(III) and nickel(II) complexes.     

Synthesis and spectral properties of new complexes between glycine and titanium(III), vanadium(III), chromium(III), iron(III), cobalt(II), nickel(II) and copper(II)

Summary Complexes of formula [MCl₃(glyH)₃] (M=Ti, V and Fe) [CrCl₃(glyH)₂H₂O], [MCl₂(glyH)₂(H₂O)₂] (M=Co and Cu) and [NiCl₂(glyH)₃H₂O] have been prepared and characterized by potentiometric curves, chemical analysis, magnetic properties, i.r. and electronic spectral data.     

Thermal decomposition of some N-oxide complexes of cobalt(II), nickel(II) and copper(II) carboxylates

Thermal decomposition of mono pyridine N-oxide complexe; of cobalt(II), nickel(II) and copper(II) propionates and mono quinoline N-oxide complex of copper(II) ben zoate has been studied by TG and DTA techniques. These dimeric complexes are stable upto 350–380 K and decompose in two stages: (i) successive elimination of the two ligand molecules (mostly endothermic); and (ii) decomposition of the resulting anhydrous metal(II) carboxylates by an exothermic multistep process in air.

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Zusammenfassung Die thermische Zersetzung der Monopyridin N-oxidkomplexe der Kobalt(II)-, Nickel(II) und Kupfer(II)-propionate sowie des Monochinolin N-oxidkomplexes von Kupfer(II)-benzoat wurden durch TG und DTA-Methoden untersucht. Diese dimeren Komplexe sind bis zu 350–380 K stabil und werden in zwei Stufen zersetzt: (i) sukzessive Eliminierung der zwei Ligandmoleküle (hauptsÄchlich endotherm); und (ii) Zersetzung der entstehenden wasserfreien Metall(II)carboxylate durch einen mehrstufigen exothermen Vorgang in Luft.

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Résumé On a étudié, par TG et ATD, la décomposition thermique des propionates des complexes mono-pyridine N-oxyde de cobalt(II), de nickel(II) et de cuivre(II) ainsi que du benzoate mono-quinoline N-oxyde de cuivre(II). Ces complexes dimères sont stables jusqu'à 350–380 K et se décomposent en deux étapes: (i) élimination successive des deux moléculesligands (la plupart du temps endothermique); et (ii) décomposition des carboxylates anhydres des métaux(II) formés par un processus en plusieurs étapes dans de l'air.

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-N- (II), (II) (II), -N- (II). 350–380 : (1) (2) .

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The authors are thankful to Dr. R. K. Dewan, Head of the Chemistry Department, University of Jammu, Jammu for providing necessary facilities in the department. The authors are also indebted to Dr. O. P. Vig, Head of the Chemistry Department, Panjab University, Chandigarh for assistance provided. One of the authors (R. K.) is grateful to University Grants Commission, New Delhi for the award of Junior Research Fellowship.     

New copper(II), manganese(III), nickel(II) and zinc(II) complexes with a chiral quadridentate Schiff base

A chiral Schiff base ligand (H₂L) was obtained by condensing 2-hydroxynaphthalene-1-carbaldehyde with substituted (1R,2R)-(–)-diaminocyclohexane. Chiral Schiff base complexes [CuL], [NiL], [ZnL] and [MnLOH] have been synthesized and characterized by elemental analyses, _M, i.r., u.v.–vis. and ¹H-n.m.r. and magnetic measurements.     

Thermal decomposition kinetics of bis(thiophene-2-carboxaldehyde thiosemicarbazonato) cobalt(II)

The thermal decomposition kinetics of thiophene-2-carboxaldehyde thiosemicarbazone complex of cobalt(II) has been studied using TG, DTG and DTA techniques. Its decomposition was subjected to critical evaluation using the equations of Freeman-Carroll, Horowitz-Metzger and Coats-Redfern and the kinetic parameters have been evaluated for each step of decomposition by the method of weighted least squares.

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Co(II) -2- , . -, - -. .

     

Three heterotrinuclear Schiff base complexes of nickel(II) with cobalt(II), copper(II) and manganese(II)

The title compounds, bis­(di­methyl­form­amide)‐1κO,3κO‐bis{μ‐2,2′‐[2,2′‐di­methyl­propane‐1,3‐diyl­bis­(nitrilo­methylidyne)]­diphenolato}‐1κ⁴N,N′,O,O′:2κ²O,O′;2κ²O,O′:3κ⁴N,N′,O,O′‐di‐μ‐nitrito‐1:2κ²N:O;2:3κ²O:N‐dinickel(II)­cobalt(II), [CoNi₂(NO₂)₂(C₁₉H₂₂N₂O₂)₂(C₃H₇NO)₂], (I), ‐copper(II), [CuNi₂(NO₂)₂(C₁₉H₂₂N₂O₂)₂(C₃H₇NO)₂], (II), and ‐manganese(II), [MnNi₂(NO₂)₂(C₁₉H₂₂N₂O₂)₂(C₃H₇NO)₂], (III), consist of centrosymmetric linear heterotrinuclear metal complexes. The three complexes are isostructural. There are three bridges across the Ni–M atom pairs (M is Co²⁺, Cu²⁺ or Mn²⁺) in each complex, involving two O atoms of a μ‐N,N′‐bis­(salicyl­idene)‐2,2′di­methyl‐1,3‐propane­diaminate ligand and an N—O moiety of a μ‐nitrito group. The coordination sphere around each metal atom, whether Co²⁺, Cu²⁺, Mn²⁺ or Ni²⁺, can be described as distorted octahedral. The Ni?M distances are 2.9988 (5) Å in (I), 2.9872 (5) Å in (II) and 3.0624 (8) Å in (III).     

Copper(II), cobalt(II), nickel(II) and zinc(II) complexes of Schiff base derived from benzil-2,4-dinitrophenylhydrazone with aniline

New Schiff base chelates of Cu(II), Co(II), Ni(II) and Zn(II) derived from benzil-2,4-dinitro-phenylhydrazone with aniline have been synthesised. Microanalytical data, molar conductance, and magnetic susceptibility values have been obtained, and IR,¹H NMR,¹³C NMR, UV-Vis, CV and EPR spectral studies have been carried out to suggest tentative structures for the complexes     

Chelate complexes of some NNO tridentate Schiff bases with iron(II), cobalt(II), nickel(II) and copper(II)

Summary The Schiff bases a-(C₅H₄N)CMe=NNHCOR (R = Ph, 2-thienyl or Me), prepared by condensation of 2-acetylpyridine with the acylhydrazines RCONHNH₂, coordinate in the deprotonated iminol form to yield the octahedral complexes, M[NNO]₂ M = Co or Ni; [NNOH] = Schiff base and the square-planar complexes, Pd[NNO]Cl. The Schiff bases also coordinate in the neutral keto form yielding the octahedral complexes (M[NNOH]2)Z2 (M = Ni, Co or Fe; Z = C104, BF₄ or N03) and complexes of the type M[NNOH]X2 (M = Ni, Co, Fe or Cu; X = Cl, Br or NCS). Spectral and x-ray diffraction data indicate that the complexes M[NNOH]X2 (M = Ni or Fe) are polymeric octahedral, as are the corresponding cobalt complexes having R = 2-thienyl. However, the cobalt complexes Co[NNOH]X2 (X = CI or Br; R = Ph or Me) and the copper complexes Cu[NNOH]CI₂ (R = Ph, 2-thienyl or Me) are five-coordinate, while the thiocyanato complex Co[NNOH](NCS)₂ (R = 2-thienyl) is tetrahedral.     

Synthesis and characterization of biacetyldihydrazone complexes of cobalt(II), copper(II), nickel(II) and iron(III)

Summary Biacetyldihydrazone (BdH) complexes [M(BdH)₃](ClO₄)₂ (M=Co^IIor Cu^II) and [M(BdH)₃](NO₃)_2,3 (M = Ni^IIor Fe^III) have been prepared and characterized by chemical analysis, conductance measurements, electronic, i.r. and e.p.r. spectral studies and magnetic subsceptibilities measurements. A mononuclear octahedral configuration is proposed for all complexes studied.     

Thermal and catalytic activity studies of some Schiff base complexes of copper(II) derived from 2-phenyl-1,2,3-triazole-4-carboxaldehyde and aniline

Thermogravimetry has been used to investigate the thermal decomposition kinetics of chloro-, bromo- and acetato complexes of 2-phenyl-1,2,3-triazole-4-carboxalideneaniline with copper(II). The decomposition process consists of two stages for all the complexes. Kinetic parameters were evaluated using the Coats-Redfern equation. Furthermore, the results of the kinetic study have been correlated with the catalytic activity of these complexes in the oxidation of hydroquinone with dioxygen.     

Synthesis and characterization of copper(II), cobalt(II), nickel(II), and iron(III) complexes with two diamine Schiff bases and catalytic reactivity of a chiral diamine cobalt(II) complex

New transition metal complexes of Co(II), Cu(II), Ni(II), and Fe(III) of the ligands 6,6′-(1E,1′E)-(4,5-dimethyl-1,2-phenylene)bis(azan-1-yl-1-ylidene)bis(methan-1-yl-1-ylidene)bis(7-hydroxy-5-methoxy-2-methyl-4H-chromen-4-one) H₂L¹ and 6,6’-(1E,1′E)-cyclohexane-1,2-diylbis(azan-1-yl-1-ylidene)bis(methan-1-yl-1-ylidene)bis(7-hydroxy-5-methoxy-2-methyl-4H-chromen-4-one) H₂L² have been prepared and characterized using physio-chemical and spectroscopic methods. The results obtained for the complexes indicated that the geometries of the metal centres are either square planar or octahedral. Cyclopropanation reactions of unactivated olefins by ethyldiazoacetate (EDA) in the presence of [L¹Cu]·H₂O, [L²Cu]·2H₂O and [L²*Co]·2H₂O as catalysts were examined. The results showed that only [L²*Co]·2H₂O can act as a catalyst for the cyclopropanation reaction of unactivated olefins with very high selectivity (up to 99% based on EDA).     

Polymetallic complexes: Part VI. Schiff base complexes of cobalt(II), copper(II), nickel(II), zinc(II), cadmium(II) and mercury(II)

Summary The doubly bidentate ON-NO donor Schiff base, prepared from salicylaldehyde and 4,4-diaminodiphenylmethane forms complexes with 11 metal: ligand stoichiometric ratios. The cobalt(II), copper(II) and nickel(II) complexes exhibit subnormal magnetic moments. All the six complexes possess high melting points and are sparingly soluble in common organic solvents. A dinuclear octahedral structure is proposed for the cobalt(II), copper(II), nickel(II) and zinc(II) complexes and a dinuclear tetrahedral configuration is suggested for the cadmium(II) and mercury(II) complexes on the basis of analytical, conductance, magnetic susceptibility, molecular weight, i.r. and electronic spectral data.