Thermal decomposition kinetics of Co(II), Ni(II), Cu(II) and Zn(II) complexes of dihydrazinium ethylenediamine-tetraacetate

Hydrazinium ethylenediaminetetraacetatometalate complexes of the type, N₂H₅ [M(Hedta)·H₂O] were subjected to systematic TG/DTG analysis. The decomposition process consists of three stages. Kinetic parameters were evaluated for each of these stages using the Coats-Redfern equation.     

Thermal decomposition of complexes of Co(II), Ni(II) and Zn(II) ions with thiosalicylic acid or ethylenediamine

The thermal decompositions of crystalline Co(II), Ni(II) and Zn(II) complexes with thiosalicylic acid or ethylenediamine were investigated via the respective thermal curves. On the basis of the decomposition temperatures, the following sequences of stabilities of the studied compounds have been proposed: 1. [Co(SR)][Ni(SR)]<[Zn(SR)]; 2. [Zn(en)₂](NO₃)₂·2H₂O<[Co(en)₂](NO₃)₂<[Ni(en)₃](NO₃)₂.     

Thermal and other properties of complexes of Mn(II), Co(II) and Ni(II) with 2,2'-bipyridine and trichloroacetates

Complexes of the general formulae Mn(2-bpy)₂(CCl₃COO)₂, Co(2-bpy)₂(CCl₃COO)₂·H₂O and Ni(2-bpy)₂(CCl₃COO)₂·2H₂O (where: 2-bpy=2,2'-bipyridine) have been prepared and characterized by VIS and IR spectroscopy, conductivity and magnetic measurements. The thermal properties of complexes in the solid state were studied under non-isothermal conditions in air atmosphere. During heating the complexes decompose via different intermediate products to the oxides Mn₃O₄, CoO and NiO. A coupled TG-MS system was used to detection the principal volatile products of thermal decomposition and fragmentation processes of obtained compounds. The principal volatile products of thermal decomposition of complexes are: H₂O⁺, CO₂ ⁺, Cl₂ ⁺ and other. This revised version was published online in August 2006 with corrections to the Cover Date.     

Electrochemical synthesis of Co(II) chelate complexes

The Co chelate complexes with acetylacetone, ethylenediaminetetraacetic acid, and its disodium salt were synthesized electrochemically and studied by the elemental analysis, UV-VIS, IR, and thermogravimetry methods in combination with isothermal heating of the samples.     

The synthesis of two new isonitrosoacetophenone derivatives and investigation of their Ni(II), Co(II), Cu(II), and Zr(IV) complexes

In the present study, two new ligands, 4-chlorobenzal-azino-isonitrosoacetophenone (L₁), 4-methylbenzal-azino-isonitrosoacetophenone (L₂) and their metal complexes were synthesized using acetophenone as a starting material. The coloured complexes were prepared by the addition of chloride salts of Ni(II), Co(II), Cu(II) and Zr(IV) ions to a solution of ligands. In conclusion, the structures of the obtained ligands and their complexes were characterized by FT-IR, and ¹H NMR spectra, AAS (atomic absorption spectrum) analysis, magnetic susceptibilities as well as elemental analysis.     

Coordination features of ditopic oxa-azamacrocycles toward Ni(II) and Co(II). Dioxygen uptake by their dinuclear Co(II) complexes

The coordination properties of the ditopic oxa-aza macrocycles L1-L3 toward Ni(II) and Co(II) have been investigated by means of potentiometric and UV-vis spectrophotometric measurements. L1-L3 contain two triamine and/or tetraamine chains separated by two dioxa chains and form both mono- and dinuclear complexes in aqueous solution. In the [ML]2+ complexes, the metal ion is coordinated by one of the two polyamine moieties, while the other does not participate in the coordination. In the dinuclear complexes each metal ion is coordinated, almost independently, to a single polyamine moiety. Under aerobic conditions the binuclear Co(II) complexes of the ligands L1-L3 are able to bind molecular oxygen, with a bridging coordination of O2 between the two metals.     

Ball milling: a green mechanochemical approach for synthesis of Ni (II), Co (II) and Cu (II) complexes

A series of Ni (II), Co (II) and Cu (II) complexes were synthesized with excellent yields via a one‐pot ball milling chelation reaction of those metals and β‐diketone. The process offers numerous advantages, such as better yield, short reaction time and mild reaction conditions. The computational studying was estimated to approve the geometry of the isolated solid compounds by applying density functional theory. The synthesized compounds were interpreted by using various spectroscopic techniques [infrared (IR), ¹H‐NMR, ¹³C‐NMR, UV–visible, electron spin resonance (ESR) and mass spectrometry] together with some physical studies (molar conductance and magnetic susceptibility). The outcomes data displayed that the (HD¹), (HD²) and (HD³) acted as neutral and/or mononegative bidentate ligands. The ESR as well as electronic spectra suggested the octahedral configuration for all isolated complexes, expect [Cu (HD2)(OAc)2]·2H₂O has square planar structure. Also, the in vitro antimicrobial assay was done by using the well diffusion method for HD¹, HD², HD³ and their complexes.     

Study of binary complexes of Cu(II), Ni(II) and Co(II) with sulfamethazine by voltammetry

Cyclic voltammetry (CV) and square-wave voltammetry (SWV) techniques have been used to study the binary complexes of Co(II), Ni(II) and Cu(II) with sulfamethazine (SMZ) at a static mercury drop electrode (SMDE) in 0.04 M Britton-Robinson (B-R) buffer. SMZ gave three peaks at 0.01, −1.32 and −1.55 V. Cu(II)-SMZ complex was recognized by a cathodic peak at −0.38 V. Ni(II)-SMZ complex was reduced at more positive potential (−0.77 V) than that of the hydrated Ni(II) ions (−1.08 V). Co(II)-SMZ complex is investigated at pH 7 and 8. The Co(II) complex at pH 7 is appeared as a shoulder at −1.19 V, whereas this peak becomes a well-separated form at pH 8. The study indicated that the SMZ serves as a catalyst in the reduction of Co(II) and Ni(II) ions. From electronic spectra data of the complexes, their stoichiometries of 1: 2 (metal-ligand) in aqueous medium are determined. The stability constants of the complexes are in agreement with the Irwing-Williams series (Co < Ni < Cu).     

Thermal analysis of ethylenediamine complexes of Ni(II) chloride

Thermal analysis of mono-, bis- and trisethylenediamine (en) complexes of Ni(II) chloride was carried out using TG, DTG and DTA techniques. The kinetic parameters were estimated from dynamic TG studies using the Coats and Redfern equation. The thermal stability of the metal-ligand (Ni-N) bond in, the complex was found to decrease with increasing Nien ratio. The DTA studies showed that the loss of en was initially endothermic but became increasingly exothermic with the progress of the decomposition. The final step in the case of all the three complexes was always composite in nature causing the loss of both Cl atoms with simultaneous oxidation of Ni to NiO. The dissociation of the Ni-en bonds appears to be regulated by the nucleation and growth mechanism. Kinetic parameters corresponding to various steps of decomposition of all the three complexes were evaluated.

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Zusammenfassung Mittels TG-, DTG- und DTA-Verfahren wurde eine Thermountersuchung des mono-, bis- und tris-Äthylendiammin (en) komplexes von Ni(II)-chlorid durchgeführt. Unter Zuhilfenahme der Gleichung von Coats und Redfern wurden die kinetischen Parameter anhand der Daten aus dynamischen TG-Untersuchungen abgeschätzt. Es wurde gefunden, daß die thermische Stabilität der Metall-Ligand Bindung (Ni-N) der Komplexe mit anwachsendem Ni:en Verhältnis absinkt. Aufgrund der DTA Untersuchungen erwies sich die Abgabe von en anfänglich als endotherm, mit fortschreitender Zersetzung jedoch als zunehmend exotherm. Bei allen drei Komplexen war der letzte Schritt immer komplexer Natur und beinhaltete die Abgabe beider Chloratome verbunden mit einer gleichzeitigen Oxidation von Ni zu NiO. Die Dissoziation der Ni-en Bindung scheint durch einen Keimbildungs- und Wachstums-mechanismus bestimmt zu werden. Die kinetischen Parameter für die einzelnen Zersetzungsschritte aller drei Komplexe wurden ermittelt.

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A research grant to LSP from the C.S.I.R. (India) and a JRF to SRN are thankfully acknowledged.     

Acid Co(II) and Ni(II) trifluoroacetate complexes: Synthesis and crystal structure

Anhydrous and partially hydrated acid trinuclear trifluoroacetates of divalent transition metals of the composition [M₃(CF₃COO)₆(CF₃COOH)₆)](CF₃COOH) and [M₃(CF₃COO)₆(CF₃COOH)₂(H₂O)₄)](CF₃COOH)₂, respectively, where M = Co (I, III) Ni (II, IV), were synthesized and studied by X-ray diffraction. Complexes I and II were obtained by crystallization from solutions of M(CF₃COO)₂ · 4H₂O in trifluoroacetic anhydride; complexes III and IV were synthesized under the same conditions with the use of 99% trifluoroacetic acid as a solvent. Crystals I are triclinic: space group $P\bar 1$ , a = 13.199(6) Å, b = 14.649(6) Å, c = 15.818(6) Å, α = 90.04(4)°, β = 114.32(4)°, γ = 108.55(4)°, V = 2611.3(19) ų, Z = 2, R = 0.0480. Crystals II are trigonal: space group $R\bar 3$ , a = 13.307(2) Å, c = 53.13(1) Å, V = 8148(2) ų, Z = 6, R = 0.1112. Crystals III are triclinic: space group $P\bar 1$ , a = 9.001(8) Å, b = 10.379(9) Å, c = 12.119(9) Å, α = 83.67(5)°, β = 72.33(5)°, γ = 83.44(5)°, V = 1068.3(15) ų, Z = 1 Å, R = 0.1031. Crystals IV are triclinic: space group $P\bar 1$ , a = 9.121(18) Å, b = 10.379(2) Å, c = 12.109(2) Å, α = 84.59(3)°, β = 72.20(3)°, γ = 82.80(3)°, V = 1080.94(40) ų, Z = 1, R = 0.0334.     

Thermal decomposition of Co(II), Ni(II), Cu(II) and Zn(II) hippurates

The hippurates of Co(II), Ni(II), Cu(II) and Zn(II) were isolated from the solution, their quantitative composition and the way of coordination of metal — ligand were determined and the conditions and products of thermal decomposition during heating in air atmosphere up to 1273 K were studied. The complexes of Ni(II), Cu(II) and Zn(II) heated lose some water molecules and then decompose to MO. The hippurate of Co(II) heated loses some water molecules and then decomposes to CoO with intermediate formation Co₃O₄.

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Zusammenfassung Aus Lösung wurden die Co(II)-, Ni(II)-, Cu(II)- und Zn(II)-Salze der Hippursäure gewonnen, ihre quantitative Zusammensetzung sowie die Art der Koordination der Metall-Ligandenbindung bestimmt. Weiterhin wurden die Bedingungen und Produkte der thermischen Zersetzung beim Erhitzen in einer Luftatmosphäre bis 1273 K untersucht. Die Komplexe von Ni(II), Cu(II) und Zn(II) verlieren beim Erhitzen ein paar Moleküle Wasser und zersetzen sich anschlieend zu MO. Co(II)-hippurat gibt beim Erhitzen einige Moleküle Wasser ab und zersetzt sich dann über die Zwischenstufe Co₃O₄ zu CoO.

     

Thermal decomposition of 6-amino-1,3-dimethyl-5-phenylazouracil complexes of Co(II), Ni(II), Cu(II) and Ag(I)

The thermal behaviour of 6-amino-1,3-dimethyl-5-phenylazouracil complexes of Co(II), Ni(II), Cu(II) and Ag(I) ions was studied by IR, thermogravimetric and differential scanning calorimetric techniques. IR spectroscopy applied to these complexes heated in air allowed the elucidation of the decomposition steps and the nature of the intermediate products. The Cu(II) complexes led to the same products on heating at 225°C [bis(1,3-dimethyl-2,4-dioxo-5-phenylazo-1,2,3,4- tetrahydropyrimidine-6-oxido)copper(II)].     

Template synthesis and physicochemical studies of 14-membered hexaazmacrocyclic complexes with Co(II), Ni(II), Cu(II) and Zn(II): a comparative spectroscopic approach on DNA binding with Cu(II) and Ni(II) complexes

A new series of 14-membered pendant arm hexaazamacrocyclic complexes of the type [MLX₂] · [M = Co(II), Ni(II), Cu(II) or Zn(II) for X = Cl; Co(II), Ni(II), Cu(II) or Zn(II) for X = NO₃] has been synthesized by metal template condensation of 1,2-phenylenediamine and 1,4-phenylenediamine with formaldehyde in methanol. The mode of bonding and overall geometry of these complexes have been deduced by elemental analyses, molar conductance values, FT-IR, ¹H-NMR, ¹³C-NMR, EPR, ESI-mass and UV–VIS along with magnetic measurement studies. The fluorescence and UV–VIS studies revealed a significant binding ability to DNA.     

Characterization and TG-MS studies of lactato and bipyridine-lactato complexes of Co(II) and Ni(II)

Two lactates and four new mixed ligand complexes with formulae Co(lact)₂·2H₂O, Ni(lact)₂·3H₂O, Co(4-bpy)(lact)₂, Co(2,4'-bpy)₂(lact)₂, Ni(4-bpy)(lact)₂·2H₂O and Ni(2,4'-bpy)₂(lact)₂ (where 4-bpy=4,4'-bipyridine, 2,4'-bpy=2,4'-bipyridine, lact=CH₃CH(OH)COO^-) were isolated and investigated. The thermal behaviour of compounds was studied by thermal analysis (TG, DTG, DTA). In the case of hydrated complexes thermal decomposition starts with the release of water molecules. The compounds decompose at high temperature to metal(II) oxides in air. A coupled TG-MS system was used to analyse the principal volatile products of thermolysis and fragmentation processes of obtained complexes. This revised version was published online in July 2006 with corrections to the Cover Date.     

Extended triple-bridged Ni(II)- and Co(II)-hydroxamate trinuclear complexes: synthesis, crystal structures, and magnetic properties

Crystal structures of new trinuclear complexes [Ni 3(mu-OAc F) 4(mu-AA) 2(tmen) 2], [Ni 3(mu-OAc F) 4(mu-BA) 2(tmen) 2], and [Co 3(mu-OAc F) 4(mu-BA) 2(tmen) 2] have been determined (OAc F = CF 3COO (-), AA = acetohydroxamate anion, BA = benzohydroxamate anion, tmen = N, N, N', N'-tetramethylethylenediamine). In each structure, the metal ions have distorted octahedral coordination and are triply bridged by one hydroxamate and two trifluoroacetate bridges. Magnetic properties of these compounds and of relative [Co 3(mu-OAc F) 4(mu-AA) 2(tmen) 2] were studied by susceptibility and magnetization measurements. It was shown that for nickel trimers the intramolecular magnetic coupling is weak ferromagnetic in the case of the complex with the AA group, and there is nearly no coupling in the case with BA group. Rather large zero field splitting was obtained for the distorted octahedral environments of the terminal nickel ions. The cobalt trimers were additionally studied by magnetic circular dichroism (MCD) measurements. The exchange interaction of the cobalt complexes is antiferromagnetic.     

Thermal behaviour of Co(II), Ni(II), Cu(II), Zn(II), Hg(II) and Pd(II) complexes with isatin-β-thiosemicarbazone

The isatin-β-thiosemicarbazone (ITC) complexes of Co(II), Ni(II), Cu(II), Zn(II), Hg(II) and Pd(II) were prepared and characterized by elemental analysis, as well as molar conductivity, magnetic susceptibility, FTIR, UV-Vis and ¹H NMR spectroscopic methods. The complexes were also studied for its thermal stability. They all behaviour as anhydrous complexes and its thermolysis passes through the stages of deamination (517–547 K) and complete thermal decomposition (619–735 K).