Thermal studies on metal complexes of 5-nitroso-pyrimidine derivatives

Four Hg(II) complexes, containing as ligands 6-amino-5-nitrosouracil (AH), 6-amino-3-methyl-5-nitrosouracil (BH) or 6-amino-1-methyl-5-nitrosouracil (CH), have been synthesized and their thermal behaviour studied by TG and DSC techniques: Hg₃Cl₆(AH)₄, HgCl₂(BH)₂· 2 H₂O, HgCl₂(BH)₂ · H₂O and HgC₂· 2 H₂O.The dehydration processes take place in only one step, with enthalpies in the range 40.2–60.0 kJ · mole^–1 H₂O.Pyrolytic processes start between 200 and 250°, in all cases the thermal stability of the corresponding pyrimidine derivative being lower than that of the free ligand. These processes finish between 600 and 750°, with no residue.

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Zusammenfassung Vier 6-Amino-5-nitrosouracil (AH), 6-Amino-3-methyl-nitrosouracil (BH) oder 6-Amino-1-methyl-5-nitrosouracil (CH) als Liganden enthaltende Hg(II)-Komplexe wurden synthetisiert: Hg₃Cl₆(AH)₄, HgCl₂(BH)₂ · 2 H₂O, HgCl₂(BH)₂ · H₂O und HgC₂ · 2 H₂O. Die Dehydratisierungsprozesse verlaufen in nur einem Schritt mit Enthalpien im Bereich von 40.2–60.0 kJ pro mol H₂O. Pyrolitische Prozesse setzen zwischen 200 und 250° ein. In allen Fällen ist die thermische Stabilität der entsprechenden Pyrimidin-Derivate geringer als die der freien Liganden. Diese Prozesse sind zwischen 600 und 750° beendet, wobei kein Rückstand zurückbleibt.

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g₃l₆()₄, gl₂( )₂ · 2 ₂O, gl₂()₂ · ₂O, g₂ · 2 ₂, — 6- -5-, — 6--3- — 6---5- . , 40.2–60.0 · ^–1 ₂. 200 250° 600–750° - . , .

     

Thermal studies on metal complexes of 5-nitroso-pyrimidine derivatives

The following cadmium(II) complexes of deprotonated 6-amino-5-nitroso-uracil (AH), deprotonated 6-amino-3-methyl-5-nitroso-uracil (BH) and neutral 6-amino-1-methyl-5--nitroso-uracil (CH) have been prepared and their thermal behaviour studied by TG and DSC techniques: CdA₂ · 3 H₂O, CdB₂ · 2 H₂O, CdB₂ and CdCl₂(CH)₂ · 2 H₂O.Dehydration processes of these complexes take place in only one step and the enthalpy values associated with them are comprised in the 42.7–80.5 kJ · mole^–1 H₂O range. The pyrolytic reactions finish in the 630–900 C temperature range, remaining as final residue in the case of CdA₂ · 3 H₂O, CdB₂ · 2 H₂O and CdB₂ complexes, cadmium oxide. The pyrolytic decomposition of CdCl₂(CH)₂ · 2 H₂O complex does not yield any residue, due to the elimination of cadmium chloride.

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Zusammenfassung Folgende Cadmium(II)-Komplexe von deprotoniertem 6-Amino-5-nitrosouracil (AH), deprotoniertem 6-Amino-3-methyl-5-nitroso-uracil (BH) und neutralem 6-Amino-1-methyl-5-nitroso-uracil (CH) wurden hergestellt: CdA₂ · 3 H₂O, CdB₂· 2 H₂O, CdB₂ und CdCl₂(CH)₂ · 2 H₂O. Das thermische Verhalten dieser Komplexe wurde mittels TG und DSC untersucht. Die Dehydratisierung der Komplexe verlÄuft in nur einem Schritt. Die Enthalpiewerte für diese Prozesse liegen im Bereich von 42.7–80.5 kJ · mol^–1 H₂O. Die pyrolytischen Reaktionen verlaufen im Temperaturbereich von 630–900C zu Ende, wobei im Falle der Komplexe CdA₂ · 3 H₂O, CdB₂ · 2 H₂O und CdB₂ Cadmiumoxid als Rückstand zurückbleibt. Die pyroytische Zersetzung von CdCl₂(CH)₂ · 2 H₂O verlÄuft wegen der Flüchtigkeit von CdCl₂ rückstandslos.

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CdA₂ · 3 H₂O, CdB₂ · 2 H₂O, CdB₂ CdCl₂(CH)₂ · 2 H₂O, A — 6--5-, B — 6--3--5- CH — 6--1--5- . . 42.7–80.5 · ^–1. 630–900, . CdCl₂(CH)₂ · 2 H₂O - , .

     

Thermal studies on metal complexes of 5-Nitrosopyrimidine derivatives

New 4-amino-5-nitroso-6-oxo-1,2,3,6-tetrahyaro-2-thiopyrimidine (TANH) complexes of Zn(II), Cd(II), Hg(II) and Hg(I) were prepared and their thermal behaviour was studied by TG and DSC techniques.The dehydration and deamination enthalpies of the corresponding complexes were calculated.

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Zusammenfassung Neue 4-Amino-5-nitroso-6-oxo-1,2,3,6-tetrahydro-2-thiopyrimidin-Komplexe (TANH) von Zn(II), Cd(II), Hg(II) und Hg(I) wurden dargestellt und ihr thermisches Verhalten mittels TG und DSC untersucht. Die Dehydratisierungs- und Deamminierungsenthalpien der Komplexe wurden berechnet.

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4--5--6--1,2,3,6--2- , , . .

     

Thermal studies on metal complexes of 5-nitrosopyrimidine derivatives

The following Zn(II), Cd(II), Hg(II) and Hg(I) complexes of 4-amino-1,6-dihydro-2-methylthio-5-nitroso-6-oxopyrimidine (MTH) have been prepared and their thermal behaviour studied by TG and DSC techniques: Zn(MT)₂·3H₂O, Cd(MT)·H₂O. Cd(MTH)Cl₂, Hg(MTH)Cl₂ and Hg₂(MT)(NO₃). The dehydration and dehalogenation enthalpy values were calculated.     

Thermal studies on metal complexes of 5-nitrosopyrimidine derivatives IV

The thermal decomposition processes of the complexes of 6-amino-5-nitrosouracil with Fe(II), Co(II), Ni(II) and Cu(II) have been studied using TG and DSC techniques. Dehydration energies have been calculated from the DSC curves.     

Thermal degradation studies on some metal hydrazinic complexes

The paper deals with the characterization of three hydrazinic complexes with Ni, Cu and Cr respectively, by means of non-isothermal thermal methods, TG, DTG and DTA, under nitrogen atmosphere in order to investigate the structure-thermostability-thermal degradation mechanism correlation. The thermal analysis made evident the degradation mechanisms characteristic of every sample in accordance with the chemical structure. The quantitative analysis by TG-DTG afforded the estimation of the metal amount in the complex on the basis of the resulting metallic oxide nature as well as of some aspects of the thermal degradation mechanism supported by mass spectral measurements. The melting points given by DTA and confirmed by the Boetius method and the initial temperatures of thermal degradation from TG-DTG-DTA afforded to ascertain the temperature range proper for using and storing the complexes under study which show potential practical applications as drugs.     

Thermal studies on metal dithiocarbamato complexes. A review

In the present review, the work done on thermal studies of metal dithiocarbamato complexes during the period 1969–1982 are given. The thermal studies include thermogravimetry, differential thermogravimetry, differential thermal analysis, differential scanning calorimetry and mass spectrometry. Fifty-two references are included.     

Thermal studies on purine complexes: XII. Thermal behaviour of some metal complexes of hypoxanthine

Some complexes of hypoxanthine with Cu(II), Ag(I), Cd(II), Hg(II), Pd(II), Rh(III) and Pt(IV) have been prepared in ethanolic, aqueous, basic or acid media and characterized on the basis of elemental analysis and IR studies. The thermal behaviour of these compounds has been studied using TG, DTG and DSC techniques. Heats of dehydration, dehalogenation and fusion have been calculated from DSC curves.     

Thermal studies of some purine compounds and their metal complexes

The mechanism of the decomposition of the entitled compounds and their complexes is studied. Adenine, its Schiff base of salicylaldehyde, and its azo resorcinol derivatives are ended with carbon. However, oxalonitrile compound is appeared as a final product for adenine acetylacetone and an intermediate for adenine. The thermodynamic parameters of the decomposition reaction were evaluated and discussed. The change of entropy values, ΔS ^#, showed that the transition states are more ordered than the reacting complexes. The thermal processes proceed in complicated mechanisms where the bond between the central metal ion and the ligands dissociates after losing small molecules such as H₂O, NH₃, or HCl. In most cases, the free radical species of the ligands are assigned to exist through decomposition mechanisms. The copper adenine and nickel salicylaldehyde complexes are ended with the metal as a final product. However, the cobalt adenine, its acetylacetone, its salicylaldehyde, cadmium and mercury guanine complexes are ended with metal oxides.     

Infrared studies of group IIB metal complexes with some imidazole derivatives

The complexes formed by zinc(II), cadmium(II) and mercury(II) halides and perchlorates with N-ethylimidazole and N-propylimidazole have been prepared and characterized by molecular conductance and i.r. spectral data down to 100 cm⁻¹. On the basis of the assignments of the metal—halogen and the metal—ligand vibrations, the stereochemistry of the compounds was inferred.     

Synthesis and physicochemical studies of metal complexes of ferrocene Schiff base derivatives

Two new Schiff bases were prepared by condensing acetylferrocene and 1,1′-diacetylferrocene with S-methyl- dithiocarbazate. Complexes of the two ligands acetylferrocene-1-hydrazono-S-methyldithiocarbazate HmaL and diacetylferrocene-1,1′-dihydrazono-S-methyldithio-carbazate H2daL, with copper(II), nickel(II) and cobalt(II) ions were isolated. The ligands coordinate to the metal ions through either their thioketone or thioenol forms. Both mono- and bis-ligand metal complexes as well as bis-metal complexes of the general formulae: [(H2daL)M]2+, [(daL)M], [(HmaL)2M]2+, [(maL)2M], [(HmaL)2MX2], [(H2daL)M2X4] and [(daL)M2X2] were prepared. All compounds under investigation were characterized and some of their physicochemical properties are reported. This revised version was published online in June 2006 with corrections to the Cover Date.     

Synthesis,characterization and antimicrobial studies on metal complexes with a naphthofuran thiosemicarbazide derivatives

Complexes of the type MLCl₂, where M?=?Co(II), Cu(II), Ni(II), Zn(II), Cd(II) and Hg(II) and L is a thiosemicarbazide ligand derived from reaction between naphthofuran-2-carboxyhydrazide and p-chlorophenylisothiocynate (NCClPT)/p-bromophenylisothiocynate (NCBrPT) characterized by elemental analysis, conductance, magnetic susceptibility measurements, UV-Vis, IR, ¹H?NMR, and ESR. The thiosemicarbazide ligands are bidentate by coordinating through the oxygen of the carbonyl group and the nitrogen of the hydrazide residue. Based on the results, we propose structures for all the metal complexes. Both the ligands and their complexes have been screened for their fungicidal and bactericidal activities.     

Solution and solid studies of some metal complexes with cytosine and its derivatives

Stability constants for the binary (1?:?1) complexes of CoII, NiII, CuII, ZnII, CdII, CaII, SrII and BaII with cytosine, cytidine, 5-bromocytosine, 5-azacytosine and 5-fluorocytosine were determined in aqueous solution (Ionic strength, μ = 0.1?mol?dm^?3 NaNO₃) potentiometrically at 25, 35 and 45°C. Experimental pH titration data were analyzed using the BEST computer program in order to evaluate formation constants of various intermediate species formed in the above binary systems. Enthalpy and entropy changes for the formation of binary complexes were calculated. On the basis of solution studies, efforts were made to prepare the binary complexes with 5-azacytosine ligand. Isolated solid complexes were characterized by different techniques and spectroscopic studies suggested a polymeric nature for the complexes, with OH and 5-azacytosine acting as bridging ligands.     

Thermal studies on purine complexes. VII. 8-theophylline derivatives and their silver(I) complexes

Four theophylline derivatives: 8-ethyltheophylline (ETH), 8-isopropyltheophylline (IPH), 8-propyltheophylline (PRH), and 8-phenyltheophylline (FTH) have been synthesized and characterized by spectroscopic techniques and thermal analysis. The melting points of these theophylline derivatives increase with the molecular weight, from 263.8°C (ETH) to 384.7°C (FTH). The values of the fusion enthalpy increase in the same order, from 28.4 kJ mol⁻¹ (ETH) to 36.5 kJ mol⁻¹ (FTH).

The interaction of these theophylline derivatives with Ag(I) has been studied by means of spectroscopic techniques, TG, DTG and DSC. In all cases, the pyrolysis of these compounds gave metallic silver.     

Solid state decomposition studies on metal salicylates. Thermal decomposition of some lanthanide salicylato complexes

The thermal stability and mechanism of thermal decomposition in air of the four lanthanide complexes of 2-hydroxybenzoic acid have been studied by TG, DSC, IR and MS techniques. An analysis of the prepared compounds show that Pr(III), Nd(III) and Tb(III) form anhydrous salicylato (Hsal)⁻ complexes while the corresponding holmium compound contains four water molecules. The TG curves show two (praseodymium, terbium), three (neodymium) or four (holmium) main stages of thermal decomposition. The most unstable among the complexes studied is Ho(Hsal)₃·4H₂O which releases four water molecules in an endothermic dehydration step. Ligand molecules decompose mainly in two stages of which the first is endothermic and is attributed to the release of the ligand acid and the second is a strongly exothermic decarboxylation process. The final decomposition product is the corresponding lanthanide(III) oxide, except in the case of terbium which decomposes to Tb₄O₇.     

Thermal studies on tris-chelate complexes of nickel

A systematic TG/DTG/DTA analysis is reported of anhydrous and heptahydrate forms of tris-phenanthroline and tris-pyridyl complexes of nickel(II), whose kinetic parameters were calculated by five different methods. The dehydration and de-ligation steps are descrete in Ni(phen)₃Cl₂ · 7 H₂O, while those in Ni(bipy)₃Cl₂ · 7 H₂O are mixed. Partial loss of the ligand is common for both hydrated and anhydrous compounds. In most cases the activation energyE _a calculated from the mechanism-non-invoking equation of Horowitz and Metzger is in good agreement with that found from the mechanism-based relation of Mampel. There is an appreciable variation in magnitude in the results obtained from the different relations for the evaluation ofE _a. It is inferred that such kinetic data are of significance in comparisons of the decomposition processes in related systems but not as absolute quantities.

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Zusammenfassung Eine systematische TG/DTG/DTA Analyse für wasserfreie und heptahydrate Formen der Tris-Phenantrolin- und Bipyridylkomplexe von Nickel(II), deren kinetische Parameter durch fünf verschiedene Methoden berechnet wurden, wird beschrieben. Die Dehydratisierung und Abspaltung der Liganden erfolgt im Ni(phen)₃Cl₂ · 7 H₂O, diskret, während sie sich im Ni(bipy)₃Cl₂ 7 H₂O überlagern. Ein teilweiser Verlust des Liganden erfolgt sowohl für hydratisierte als auch für wasserfreie Verbindungen. In den meisten Fällen ist die aus dem Mechanismus der Nicht-Invokationsgleichung von Horowitz und Metzger berechnete AktivierungsenergieE _a in guter Übereinstimmung mit der berechneten aus dem auf dem Mampelschen Zusammenhang beruhenden Mechanismus. Innerhalb der verschiedenen, zur Bewertung vonE _a gesuchten Zusammenhänge, besteht eine deutliche Variation in der Größe. Es wird daraus abgeleitet, daß solche kinetische Daten hinsichtlich des Vergleichs der Zersetzungsprozesse verwandter Systeme von Bedeutung, doch nicht als absolute Werte zu betrachten sind.

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// , . Ni ( )₃Cl₂. 7H₂O₂ — , Ni ()₃Cl₂. 7₂ - . . E _a, , , . E _a, E _a. , .

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We are grateful to Prof. V. K. Phansalkar, Head of the Department of Chemistry, for the facilities and encouragement given during the work. We are also grateful to Prof. A. K. Chakraborty, IACS, Calcutta, for providing the facilities for the thermal studies. One of the authors (P. S. D.) is grateful to CSIR, New Delhi for financial assistance during this work.     

Synthesis and characterization of 5-substituted 8-hydroxyquinoline derivatives and their metal complexes

5-Aminomethyl-8-hydroxyquinoline (QN) was synthesized as a scaffold to generate dimers, trimers, and tetramer metalloquinolates. Starting from QN, a series of 5-substituted 8-hydroxyquinoline derivatives conjugated with small bioactive molecules were synthesized. Absorption and emission spectra indicate that these QN derivatives chelate well with metal ions, which may serve as a new platform to explore the applications of metalloquinolates for a variety of potential applications.     

Thermal decomposition of metal complexes V. Lanthanide(III) complexes of benzo-15-crown-5

Thermal dissociation reactions of lanthanide(III) nitrates and thiocyanates solid complexes of the cyclic polyether benzo-15-crown-5 were studied in dynamic atmosphere of dry nitrogen and under reduced pressure (5·10^?2 mm Hg). The complexes of lanthanide nitrates undergo dissociation with ligand decomposition while from those of lanthanide thiocyanates the ligand is released undecomposed. Values of enthalpy change and “activation energy” for the dissociation reactions of the complexes with lanthanide thiocyanate were obtained and briefly discussed.     

Thermal analysis of metal complexes,III

On the basis of the thermal investigation of Mpy_nX _z mixed complexes (where M=Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺; py=pyridine; or-, - and-picoline; X=Cl^–, Br^–, I^–, OCN^–, SCN^–, NO ₃ ^– , SO ₄ ^2– ; andn=2,3,4,6;z=1,2), factors influencing the stability of the metal-pyridine-N bond have been determined.On the basis of the measured magnetic susceptibilities the symmetry of the coordina tion sphere of the central atom has been established in the intermediate products formed by the thermal decomposition of cobalt(II) complexes.

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Zusammenfassung Aufgrund derivatographischer Untersuchungen von Mischkomplexen des Typs Mpy_nX_z (M=Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺; py=Pyridin,, und Piccolin; X=Cl^–, Br^–, I^–, OCN^–, SCN^–, NO ₃ ^– , SO ₄ ^2– ;n=2, 3, 4, 6;z=1, 2) wurden die die StabilitÄt der Metall-Pyridin-N Bindung beeinflussenden Faktoren geprüft. Durch Messung der magnetischen SuszeptibilitÄten wurde die Symmetrie der KoordinationssphÄre des Zentralatoms des bei der thermischen Zersetzung entstehenden Kobalt(II)-komplexes ermittelt.

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Résumé On a examiné des complexes du type Mpy _n X _z (où M=Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺; py=pyridine,-,- et-piccoline; X=Cl^–, Br^–, I^–, OCN^–, SCN^–, NO ₃ ^– , SO ₄ ^2– ;n=2, 3, 4, 6;z=1, 2) dans le but de déterminer les facteurs ayant une influence sur la stabilité de la liaison métal-pyridine-N. Par mesure des susceptibilités magnétiques, on a pu établir dans la cas des complexes du Co²⁺ la sphère de coordination de l'atome central pour les phases intermédiaires produites par décomposition thermique.

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_nz ( M=n²⁺, ²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺; py= , , ; X=Cl^–, Br^–, I^–, OCN^–, SCN^–, NO₃ ^–, SO ₄ ^2– ; n=2, 3, 4, 6; z=1, 2) , --N. , (II).

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Previous paper of the series: G. Liptay, K. Burger, E. Papp Molnár, Sz. Szebeni, F. Ruff: J. Inorg. Nucl. Chem. 31 (1969) 2359.

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We are indebted to Miss é. Szabó for technical assistance.     

Thermal decomposition of metal complexes with thioureas

Thermal decomposition of methyl and dimethylthiourea complexes of several transition metals and of cadmium complexes with several thioureas and ureas were studied by thermogravimetric analysis in air and vacuum and stability relations established. In vacuum, dimethylthiourea complexes decompose to a mixture of metal chloride and sulfide; the organic products include dimethylthiourea, methylisothiocyanate, HCl and polymerized material. In air, intermediates are formed in which part of the organic ligand is retained followed by complete decomposition to inorganic salts at higher temperatures. The intermediate contains little sulfur and appears to be a substituted urea compound.