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.     

Kinetics of annealing of nitrite in gamma-irradiated cis-nitrato bis-(ethylenediamine) Ni(II) perchlorate and trans-dinitrato bis-(ethylenediamine) Ni(II)

The kinetics of annealing of nitrite in γ-irradiated (1.0 MGy) cis-nitrato bis-(ethylenediamine) Ni(II) perchlorate and trans-dinitrato bis-(ethylenediamine) Ni(II) is explored. The data reveal that annealing of nitrite, NO^-₂ between 130.0 and 170.0°C in both the complexes follows a combination of one first order and one second order process. The extent of recombination in trans-dinitrato complex (ϕ = 0.89) is higher than that in the cis-nitrato compound (ϕ = 0.69), though the radiolytic decomposition is in the reverse order. The data are analysed in the light of theories of diffusion controlled mechanics like Fletcher-Brown, Waite and Vand-Primak treatment.     

Thermal analysis of Ni(II) N-methylimidazole compounds

In this study the thermal decomposition of compounds with the formula Ni(NMIz)_nX₂ (NMIz=N-methylimidazole,n= 6, 4, 2 or 1 andX= Cl, Br or I) has been investigated with the aid of differential scanning calorimetry (DSC), thermogravimetry (TG), evolved gas analysis (EGA) and X-ray powder diffraction in the temperature region 20–500°. The reaction steps were obtained with TG. The intermediate products of the reactions were also confirmed by high-temperature Guinier-de Wolff X-ray photographs.The decomposition enthalpies were calculated from differential scanning calorimetry analysis. The enthalpies were compared with the data from a previous study of the imidazole compounds in order to get more information about the hydrogen bonding in the imidazole compounds. The hydrogen-bonding is stronger for smaller anions and decreases the decomposition enthalpy for imidazole compounds. The decomposition enthalpy ofN-methylimidazole compounds is hardly influenced by the anion size.

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Zusammenfassung In diesen Untersuchungen wird über die thermische Zersetzung von Verbindungen der Formel Ni(NMIz)_nX₂ (NMIz=N-methylimidazol,n=6, 4, 2 oder 1 undX=Cl, Br oder I) mit Hilfe der Differential-Scanning-Kalorimetrie (DSC), der Thermogravimetrie (TG), der Analyse der entwickelten Gase (EGA) und der Röntgenpulverdiffraktion im Temperaturbereich von 20 bis 500° berichtet. Die Reaktionsstufen wurden durch TG erhalten. Die Zwischenprodukte der Reaktionen wurden durch Guinier-de Wolff-sche Hochtemperatur-Röntgenaufnahmen bestätigt.Die Zersetzungsenthalpien wurden aus den Ergebnissen der Differential-Scanning-Kalorimetrie berechnet. Die Enthalpien wurden mit den Angaben aus einer vorangegangenen Untersuchung der Imidazolverbindungen verglichen, um mehr Informationen über die Wasserstoffbindungen in den Imidazolverbindungen zu erhalten. Die Wasserstoffbindung ist für kleinere Anionen stärker und setzt die Zersetzungsenthalpie der Imidazolverbindungen herab. Die Zersetzungsenthalpie derN-Methylimidazolverbindungen wird durch die Grösse des Anions kaum beeinflusst.

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Résumé La décomposition thermique des composés de formule Ni(NMIz)nX₂ (NMIz=N-méthyl-imidazole,n= 6, 4, 2 ou 1 etX= Cl, Br ou I) a été étudiée par analyse calorimétrique différentielle (DSC), thermogravimétrie (TG), analyse des gaz émis (AGE) et diffraction sur poudre des rayons X dans l'intervalle des températures comprises entre 20 et 500°.Les étapes réactionnelles ont été suivies par TG. Les phases intermédiaires formées ont été déterminées par rayons X à hautes températures d'après la méthode de Guinier-de Wolff.Les enthalpies de décomposition ont été calculées à partir des courbes DSC. On a comparé les valeurs ainsi trouvées à celles d'une étude préalable des composés de l'imidazole, afin d'obtenir plus d'informations sur les liaisons d'hydrogène dans les composés de l'imidazole. Les liaisons d'hydrogène sont plus fortes si les anions sont petits et diminuent l'enthalpie de décomposition des composés de l'imidazole. L'enthalpie de décomposition des composés duN-méthyl-imidazole n'est presque pas influencée par la taille de l'anion.

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Ni(NMIz)_nX₂ (NMIz=N-, =6,4,2 1, X=l, r I) , (), 20–500°. . , - -. . . . N- .

     

Ternary complexes of the Cu(II) and Ni(II) chelates of edta and dcta with cyanide and ethylenediamine

The formation of the ternary complexes CuEDTA(en)(2-), CuEDTA(CN)(3-), CuDCTA(CN)(3-), NiDCTA(CN)(3-) and NiEDTA(en)(2-) has been established spectrophotometrically. The stability constants found were log K = 2.87 +/- 0.03, 3.76 +/- 0.06, 2.64 +/- 0.35, 2.41 +/- 0.21 and 2.74 +/- 0.35 respectively. For the system CuDCTA(2-) + en no ternary complex was observed, instead Cu(en)(2)(2+) was formed. No reaction was found for the systems CoEDTA(2-) + N(3)(-), CoDCTA(2-) + N(3)(-), NiDCTA(2-) + en, NiDCTA(2-) + phen, NiEDTA(2-) + phen, NiDCTA(2-) + N(3)(-), NiEDTA(2-) + N(3)(-), CrEDTA(-) + NH(3), CrEDTA(-) + CN(-), CuEDTA(2-) + N(3) and CuEDTA(2-) + N(3)(-). The systems CoEDTA(2-) + en and CoDCTA(2-) + en involve more than one equilibrium. The absorption spectra of the ternary complexes between 500 and 850 nm are reported.     

Nickel(II) and Copper(II) complexes of sulphamide and ethylenediamine

Summary The following ethylenediamine(sulphamide)nickel(II) and ethylenediamine(sulphamide)copper(II) complexes were prepared: Ni(en)₃(H₂Su)Cl₂, in which H₂Su is not coordinated; Ni(en)₂(H₂Su)Cl₂ , Ni(en)₂(HSu)Cl · EtOH, Ni(en)₂(HSu)₂,Ni(en)₂(HSu)₂(H₂Su)₂ · EtOH, Cu(en)₂(HSu)₂(H₂Su) · O.5EtOH, in which the sulphamide molecule, H₂Su, or the sulphamidato anion [HSu] are totally or partially coordinated. The comparison of the i.r. spectra of these complexes with those of H₂ Su and NaHSu and with those of the M(en)₂Cl₂ complexes permits the isolation of the sulphamide or sulphamidato (SO₂) and (SN₂) bands which show oxygen-coordination of these ligands to the metal. Some (MO) bands were identified in the far i.r. region.     

Thermal decomposition of octahedral Ni(II) complexes with acetone 1-naphthoylhydrazone

The thermal decompositions of acetone 1-naphthoylhydrazone (L) and its octahedral complexes with Ni(II), with the general formula NiL₂X₂ (X=Cl, Br, NO₃ and NCS), were studied in air and nitrogen atmospheres. It was established that the organic ligand is decomposed in an exothermic processes, which is followed by oxidation of the decomposition fragments by atmospheric oxygen. At temperatures below 640°, all the complexes decompose completely, yielding NiO as the final product, which was confirmed by its X-ray analysis. From the difference between the enthalpy changes for the decompositions of the complexes and of the ligand itself, the nature of the final oxide, and the crystal field splitting parameters obtained from optical measurements, the corresponding stabilization energies were determined.

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Zusammenfassung In Luft- und Stickstoffatmosphäre wurde die thermische Zersetzung von Azeton-1-naphthoylhydrazon (L) und seinen oktaedrischen Komplexen mit Ni(II) mit der allgemeinen Formel NiL₂X₂ (mit X=Cl, Br, NO₃ und NCS) untersucht. Es wurde festgestellt, daß der organische Ligand in einem exothemen Prozeß einer Zersetzung und einer anschließenden Oxydation der Zersetzungsprodukte durch Luftsauerstoff unterliegt. Unterhalb 640° zerfällen alle Komplexe vollständig und liefern NiO als Endprodukt, welches mittels Röntgendiffraktionsanalyse identifiziert wurde. Aus dem Unterschied zwischen Enthalpieänderungen für die Zersetzung der Komplexe und des Liganden selbst, aus der Art der erhaltenen Oxide und aus den Parametern der durch optische Messungen bestimmten Kristallfeldaufspaltung wurden die entsprechenden Stabilisierungsenergien bestimmt.

     

Thermal decomposition of octahedral Ni(II) complexes with 1-Naphthylacetic acid hydrazide

The thermal decompositions of the octahedral complexes of Ni(II) with 1-naphthylacetic acid hydrazide (L), of the type NiL_nX₂·mH₂O, wheren=2 and 3,m=2 and 4, andX=Cl, Br, I, NCS, OAc and 1/2 SO₄, were studied in both air and nitrogen atmospheres at temperatures up to 1000 C. The most probable mechanism of the process was proposed.

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Zusammenfassung In dieser Arbeit wurde die thermische Zersetzung oktaedrischer Ni(II)-Komplexe mit Hydraziden der 1-Naphthylessigsäure (L) des Types NiL_n X ₂·mH₂O untersucht, wobein=2 bzw. 3,m=2 bzw. 4 undX=Cl, Br, I, NCS, OAc bzw. 1/2 SO₄ ist. Die thermische Zersetzung wurde in Luftbzw. Stickstoffatmosphäre bis zu Temperaturen von 1000 C durchgefürt und der wahrscheinlichste Mechanismus des Prozesses gegeben.

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1- (L) NiL_n X ₂·mH₂O, n=2 3,m=2 4, X=Cl, Br, I, NCS, OAc 1/2SO₄. 1000. .

     

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 behavior of Co(II) and Ni(II) hydroxycarboxylate complexes obtained by two original synthesis methods

This paper presents a facile and rapid synthesis route of metallic Ni and Co nanocrystallites at ~150 °C in the mixture composed of the corresponding metal nitrates and 1,3-propanediol, as reducing agent. The metal oxides NiO, CoO, Co₃O₄ nanocrystallites were, also, successfully synthesized by thermal decomposition at 300 °C of the hydroxycarboxylate coordination products, obtained in the redox reaction between 1,3-propanediol and Ni(II) and Co(II) nitrates. The formation of the Ni(II) and Co(II) hydroxycarboxylate complexes depends on the diol which generates the carboxylate anion, the transition metal and the process parameters. Ni(II) and Co(II) nanocomposites were also synthesized by thermal decomposition of the complex combinations formed within the pores of the hybrid silica gels. One of the purposes of the present study was to investigate the phase constitution of the composites obtained in similar synthesis conditions, from Ni(II) and Co(II) complex combinations embedded in silica gels. These gels were submitted to various thermal treatments and the changes occurring during these treatments were described by X-ray diffraction. Thermal analysis is an excellent tool for the study of the processes implied in the formation and decomposition of the Co(II) and Ni(II) carboxylate complexes. X-ray diffraction evidenced the nanometer sized metal and/or metal oxide phases.     

Copper(II) halide complexes with deprotonated N-(2-hydroxyethyl)ethylenediamine

Dimeric complexes of the type (CuLX)₂, where L is deprotonated N-(2-hydroxyethyl)ethylenediamine and X is either the chloride or bromide anion, were prepared. The complexes were characterized by elemental analyses, IR spectra, electronic spectra, ESR spectra and magnetic moments. Both complexes exhibit antiferromagnetic interactions.     

Rhodium(III), palladium(II) and platinum(II) complexes of Bis(o-aminobenzenesulfonyl)ethylenediamine

New complexes of the formulae K₃[RhL ₃]·2 H₂O, [PdL]·H₂O and [M(LH₂)Cl₂] [whereM = Pd, Pt andLH₂ = bis(o-aminobenzenesulfonyl)ethylenediamine] have been prepared and characterized by conductivity measurements, thermogravimetric analysis, X-ray powder patterns and IR, Ligand Field and¹H-NMR spectroscopy.

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Rhodium(III), Palladium(II)- und Platin(II)-Komplexe mit Bis(o-aminobenzolosulfonyl)ethylendiamin (Kurze Mitteilung)

Zusammenfassung Neue Komplexe der allgemeinen Formeln K₃[RhL ₃]·2H₂O, [PdL]·H₂O und [M(LH₂)Cl₂] mitM = Pd, Pt undLH₂ = Bis(o-aminobenzolosulfonyl)ethylendiamin wurden dargestellt und mit Konduktionsmessungen, thermogravimetrischen Analysen, Röntgenstrukturanalysen, IR, Ligandfeld- und¹H-NMR-Spektroskopie charakterisiert.

     

Electrochemical Polymerization of Ni(II) and Pd(II) Complexes with 1,2-Bis(o-aminobenzylidene)ethylenediamine

Polymers based on the Pd(II) and Ni(II) complexes with 1,2-bis(o-aminobenzylidene)ethylenediamine and exhibiting conducting properties are synthesized. The kinetic regularities of polymer formation on solid substrates and dependence of the rate of charge diffusion in a bulk of polymer matrix on the polymer thickness are established.     

A combined theoretical and thermal analysis study on the solid state linkage isomerization of Ni(II)-nitrite complexes with ethylenediamine derivatives*

Solid state stepwise nitro–nitrito linkage isomerization of trans-[dinitrobis(ethylenediamine)nickel(II)], [Ni(en)₂(NO₂)₂] (N,N-en), trans-[dinitrobis(N,N′-dimethylethylenediamine)nickel(II)], [Ni(N,N′-dmen)₂(NO₂)₂] (N,N-dmen), and trans-[dinitritobis(N,N-dimethylethylenediamine)nickel(II)], [Ni(N,N-dmen)₂(ONO)₂] (O,O-udmen) were investigated by performing non-isothermal differential scanning calorimetry (DSC) analyses and the thermodynamic and thermokinetic parameters of isomerization were determined using DSC curves. Both N,N-en and N,N-dmen DSC curves show an endothermic peak at elevated temperatures, attributed to dinitro-to-dinitrito linkage isomerization. Similar exothermic peaks were observed in the cooling cycle, assigned to the reverse dinitrito-to-dinitro isomerization. The O,O-udmen isomer is more stable than the corresponding dinitro one at ambient temperatures, but an exothermic dinitrito-to-dinitro isomerization occurs upon cooling down to ?70 °C and reverts endothermically to dinitrito isomer upon heating up to ambient temperature. The overlapping DSC peaks associated with stepwise linkage isomerization were resolved using nonlinear fitting method. The peak temperature and the enthalpy changes of linkage isomerization are inversely dependent on the steric hindrance provided by diamine ligands, which increases in the order udmen > dmen > en. The results showed that the steric factor of the co-ligands also influences the kinetic parameters of isomerization, so that more bulky ligand substituent leads to higher isomerization rate constants. A DFT and TD-DFT calculations have been carrid out on both dinitro complexes of this investigation .     

Thermoanalytical investigations of tris(ethylenediamine)nickel(II) oxalate and sulphate complexes

Investigations on the thermal behaviour of [Ni(en)₃]C₂O₄·2H₂O and [Ni(en)₃]SO₄ have been carried out in air and helium atmosphere. Simultaneous TG/DTA coupled online with mass spectroscopy (MS) in helium atmosphere detected the presence of H₂, O, CO, N₂/CH₂=CH₂ and CO₂ fragments during the decomposition of tris(ethylenediamine)nickel(II) oxalate and H₂, O, NH, NH₂, NH₃ and N₂/CH₂=CH₂ fragments for tris(ethylenediamine)nickel(II) sulphate complex. The thermal events during the decomposition were monitored by temperature-resolved X-ray diffraction. In air, both the complexes give nickel oxide as the final product of the decomposition. In helium atmosphere, tris(ethylenediamine)nickel(II) oxalate gives nickel as the residue, whereas tris(ethylenediamine)nickel(II) sulphate gives a mixture of nickel and nickel sulphide phases as the final residue. Kinetic analyses of these complexes by isoconversional methods are discussed and compared.     

Thermal behaviour of new Ni(II) and Cu(II) complexes with macrocyclic ligands functionalised with 1,2,4-triazole

The investigations concerning the thermal behaviour of a series of Ni(II) and Cu(II) complexes of type [NiLCl₂]·mH₂O ((1) L:L₁, m=6; (3) L:L₂, m=4) or [CuLCl]_nCl _n ·mnH₂O ((2) L:L₁, m=6; (4) L:L₂, m=4) are presented. The ligands L(1) and L(2) have been synthesised by template condensation of 3,6-diazaoctane-1,8-diamine or 1,2-diaminoethane with formaldehyde and 2-amino-4H-1,2,4-triazole. The bonding and stereochemistry of the complexes have been characterised by IR, electronic and magnetic studies at room temperature. The in vitro qualitative and quantitative antimicrobial activity assays showed that the complexes exhibited variable antimicrobial activity against planktonic as well as biofilm embedded Gram-negative, Gram-positive and fungal strains. The thermal behaviour provided confirmation of the complexes composition as well as the number and nature of water molecules and the intervals of thermal stability.     

Thermal behaviour of nickel(II) sulphate,nitrate and halide complexes containing ammine and ethylenediamine as ligands

Thermal behaviour of nickel amine complexes containing SO₄ ²⁻, NO₃ ⁻, Cl⁻ and Br⁻ as counter ions and ammonia and ethylenediamine as ligands have been investigated using simultaneous TG/DTA coupled with mass spectroscopy (TG/DTA–MS). Evolved gas analyses detected various transient intermediates during thermal decomposition. The nickel ammonium sulphate complex produces NH, N, S, O and N₂ species. The nickel ammonium nitrate complex generated fragments like N, N₂, NO, O₂, N₂O, NH₂ and NH. The halide complexes produce NH₂, NH, N₂ and H₂ species during decomposition. The ligand ethylenediamine is fragmented as N₂/C₂H₄, NH₃ and H₂. The residue hexaamminenickel(II) sulphate produces NiO with crystallite size 50 nm. Hexaammine and tris(ethylenediamine)nickel(II) nitrate produce NiO in the range 25.5 nm and 23 nm, respectively. The halide complexes produce nano sized metallic nickel (20 nm) as the residue. Among the complexes studied, the nitrate containing complexes undergo simultaneous oxidation and reduction.     

Thermal analysis of nickel(II) complexes with some N-monosubstituted ethylenediamines

The thermal analysis of complexes of N-R-ethylenediamine, where R=ethyl, propyl, 2-hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl, with the halides, thiocyanate and sulphate of nickel is reported. The procedural decomposition temperatures of the complexes are given and considered in relation to the structures of the compounds.

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Zusammenfassung Es wurde über die thermoanalytische Prüfung der Komplexe von N-R-Äthylendiamin (R=Äthyl, Propyl, 2-HydroxyÄthyl, 2-Hydroxypropyl und 3-Hydroxypropyl) mit Nickelhalogenid, -sulfat und -rhodanid unter Angabe der entsprechenden Zersetzungstemperaturen in Zusammenhang mit den strukturalen Umwandlungen der Verbindungen berichtet.

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Résumé On communique les résultats relatifs à l'analyse thermique des complexes formés par la N-R-éthylènediamine (R=éthyl, propyl, hydroxy-2 éthyl, hydroxy-2 propyl et hydroxy-3 propyl) avec les halogénures, le thiocyanate et le sulfate de nickel. On a cherché à établir une relation entre la température observée pour la décomposition et la structure des composés.

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N-R-, R= , , 2-, 2- 3-, , . .

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We wish to thank the Science Research Council for a grant to B. L. O'Leary.     

Counterdisproportionation between cationic Ni(II) and phosphine Ni(0) complexes

The interaction of Ni(II) bis-tetrafluoroborate complexes [Ni(Dppe)₂](BF₄)₂ and [Ni(CH₃CN)₆](BF₄)₂ (where Dppe = 1,2-bis(diphenylphosphino)ethane)) with Ni(0) phosphine complexes Ni(Dppe)₂ and Ni(PPh₃)₄ in 1 : 1 mixture of toluene-acetonitrile was studied by the EPR method. The counter-disproportionation was shown to occur in a solution between the cationic Ni(II) complexes and the Ni(0) complexes to give Ni(I) complexes almost in quantitative amounts. The structures of the cationic Ni(I) complexes obtained were found to depend on both the solvent nature and the presence of a free phosphine in a solution.