First synthesis and characterization of platinum(II) and palladium(II) complexes of some β-carboline hydrochloride alkaloids and their decomposition products in DMSO

Summary Platinum(II) and palladium(II) complexes of general formulatrans-[MCl₂LL] (M=Pt or Pd, L, L=-carboline; M=Pt, L=-carboline, L=ethene; -carboline alkaloids are harmaline, harmine, harmalol as hydrochloride derivatives) have been prepared for the first time. The structures were assigned and identified on the basis of their CHN analyses, i.r. and¹H n.m.r. spectra. The decomposition products of these complexes in DMSO have been described.     

Oxidative polymerization of durene and diphenyl oxide in the presence of palladium(II) and heteropolyacids

The possibility of obtaining tetramers from durene or diphenyl oxide in the presence of H₅PMo₁₀V₂O₄₀, a reversible oxidant, and palladium acetate as catalyst is demonstrated.

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— H₅PMo₁₀V₂O₄₀ .

     

The thermal decomposition reactions of bis-(pyridine-2-aldoxime)-copper(II) complexes

The thermal properties of some complexes of copper(II) with pyridine-2-aldoxime (HPAO), where the ligand appears either as the ion (PAO^–) or as a neutral molecule, were determined in vacuo and in dynamic nitrogen and oxygen gas atmospheres. The study was carried out by thermoanalytical (TG, DTG. DTA), spectroscopic and spectrometric (UV-visible, IR, diffuse reflectance, mass) techniques.The initial decomposition temperature is influenced by the number of acid hydrogens in the complex; the thermal stability sequence in vacuo is: [Cu(PAO)₂H]Cl > [Cu(PAO)₂H₂]Cl₂ > [Cu(PAO)₂]The thermal decomposition reactions occur in several separate steps, the first of which gives rise to partial ligand decomposition, the reduction of copper(II) to copper(I), and the conversion of the residual pyridine-2-aldoxime into acid amide.

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Zusammenfassung Die thermischen Eigenschaften einiger Komplexe von Kupfer(II) mit Pyridin-2-aldoxim (HPAO), in denen der Ligand entweder als Ion (PAO^–) oder als neutrales Molekül vorliegt, wurden im Vakuum und in dynamischer N₂- und O₂-Atmosphäre ermittelt. Zur Untersuchung wurden thermoanalytische (TG, DTG, DTA) und spektrometrische (UV-sichtbar, IR, diffuse Reflektionsspektrophotometrie, Massenspektrometrie) Techniken herangezogen. Die Temperatur, bei der die Zersetzung beginnt, wird durch die Zahl der sauren Wasserstoffatome im Komplex beeinflußt; für die thermische Stabilität im Vakuum gilt die Reihenfolge [Cu(PAO)₂H]Cl > [Cu(PAO)₂H₂]Cl₂ > [Cu(PAO)₂]. Die thermischen Zersetzurigsreaktionen verlaufen in mehreren diskreten Schritten, wobei der erste von diesen eine partielle Zersetzung des Liganden, die Reduktion von Kupfer(II) zu Kupfer(I) und die Konversion des verbleibenden Pyridin-2-aldoxims in das Säureamid in sich einschließt.

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-2- ( ), (-), . (, , ) , - , , - . , [Cu(PAO)₂H]CI > [Cu(PAO)₂H₂]Cl₂ > [Cu(PAO)₂] , , -2- .

     

Syntheses and properties of mixed dinuclear copper(II) complexes with heterocyclic dithiocarbamates and a cyclic octadentate tertiary amine

Five new Cu^II complexes of general formula [Cu₂(Rdtc)tpmc](ClO₄)₃, (1)–(5), where tpmc and Rdtc ^– refer to N,N,N,N-tetrakis(2-pyridylmethyl)-1,4,8,11-teraazacyclotetradecane and piperidine- (Pipdtc), 4-morpholine- (Morphdtc), 4-thiomorpholine- (Timdtc), piperazine- (Pzdtc) or N-methylpiperazine- (N-Mepzdtc) dithiocarbamates, respectively, have been prepared. Elemental analyses, conductometric and magnetic measurements, u.v./vis, i.r., e.p.r. and mass spectroscopy have been employed to characterize them. The complexes adopt an exo coordination of Cu^II ions and tpmc. The dithiocarbamate ion joins both the sulphur and the copper atoms acting as a bridging ligand The presence of different heteroatoms in the piperidine ring influences the (C=N) and (C=S) vibrations which decrease in the order of the complexes: Pipdtc>N-Mepipdtc>Pzdtc>Morphdtc>Timdtc ligands. Attention has been paid to the detailed mechanism of the mass spectral fragmentation of the complexes. The g _eff factors of the complexes have been also estimated by e.p.r. spectra. Finally, the complexes obtained demonstrate microbiologycal activity against some bacteria.     

Interaction of PM12?nVnO40?(3+n) (M=Mo, W) heteropoly complexes with nitrogen oxide

In aqueous solution, PM_12–nV_nO₄₀ ^–(3+n) (M=Mo,W) hetero-polyanions provide a much faster oxidation of NO than mononuclear VO ₂ ⁺ ions, yielding HNO₂, NO ₃ ^– and reduced HPA.

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, PM_12–nV_nO₄₀ ^–(3+n) (M=Mo,W) , VO ₂ ⁺ , NO HNO₂ NO ₃ ^– .

     

Reactivity of the Peroxo Complexes of Copper(II) Hydroxide

In the interaction with H₂O₂ in an alkaline medium, Cu(OH)₂ forms terminal Cu–OOH and bridging peroxo complexes with the -1,1 and -²:² structures. It was found that the terminal peroxide is active in the reactions of H₂O₂ decomposition, diphenol oxidation, and nitrile conversion into acid amides. The promoting effect of ammonia on these reactions was found. A possible mechanism is discussed.     

Thermal decomposition of Cu(I) phosphine complexes

The thermal decomposition of Cu(I) phosphine complexes of the general types (CuXPPh₃)₄, [CuX(PPh₃)₂] and [CuX(PPh₃)₃] was investigated.The thermal decomposition of (CuXPPh₃)₄, where X denotes Cl^–, Br^–, I^–, NO ₃ ^– and PPh₃=P(C₆H₅)₃, occurs with formation of a phosphine oxide intermediate. For the remaining complexes this intermediate was not proved in the thermal decomposition.

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Zusammenfassung Die thermische Zersetzung der Cu(I)-Phosphinkomplexe vom allgemeinen Typ (CuXPPh₃)₄ und [CuX(PPh₃)₂], wie auch [CuX(PPh₃)₃] wurde untersucht. Die thermische Zersetzung von (CuXPPh₃)₄, wobei X=Cl^–, Br^–, I^– und NO ₃ ^– bedeutet und PPh₃=P(C₆H₅)₃, verläuft unter Bildung eines Phosphinoxid Zwischenproduktes, bei den übrigen Komplexen konnte dieses im Laufe der thermischen Zersetzung nicht nachgewiesen werden.

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Résumé On a étudié la décomposition thermique des complexes phosphine-Cu(I) de formule générale (CuXPPh₃)₄, [CuX(PPh₃)₂], [CuX(PPh₃)₃]. La décomposition thermique de (CuXPPh₃)₄, où X désigne Cl^–, Br^–, I^– et NO ₃ ^– , et PPh₃=P(C₆H₅)₃, s'effectue avec formation d'un oxyde de phosphine intermédiaire; avec les autres complexes, cet intermédiaire n'a pas été mis en évidence au cours de la décomposition thermique.

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(CuXPPb₃)₄ [CuX(PPh₃)₂] [CuX(PPh₃)₃]. (CuXPPh₃)₄, X=Cl^–, Br^–, I^–, NO ₃ ^– , PPh₃=(₆₅)₃ . .

     

Mechanism of hydrogenolysis and isomerization of oxacyloalkanes on metals, V. Selectivities of metal catalysts in ring-opening reactions of oxiranes

The deoxygenation of methyloxirane to propene and its isomerization to oxo compounds on a Ni/SiO₂ catalyst were studied in a pulse microreactor, in the presence of H₂ as carrier gas, at 473 K. It was found that the deoxigenation leads to the creation of new types of active centers (Lewis acid site-basic site), which cause a change in the direction of ring opening. The differences in regioselectivity observed between Ni and Cu, and Pt and Pd, can be explained by the different affinities of the metals for oxygen. This finding can be generalized to other oxygen-containing compounds.

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=qa Ni/SiO₂ 473 . , - - , . Ni Cu, Pt Pd . .

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Part IV: J. Catal. (to be published)     

ESR study of Jahn-Teller distortions and the structure of Cu(II) complexes in [Cu(bipy)2X](ClO4) and [Cu(phen)2X](ClO4)

The Cu(II) complexes in [Cu(bipy)₂X](ClO₄) and [Cu(phen)₂X](ClO₄) were studied by ESR spectroscopy at =9.8 GHz and optical absorption at 7000–20,000 cm^–1. The axially symmetrical g factors, corresponding to the g, were established for the distorted trigonal bipyramidal coordination of Cu(II) with C _2v symmetry. Analysis of the possible vibrational distortions of the complex showed that the axial symmetry of the g factor is a consequence of orientational averaging realized for an electronic vibrational state with a two-well adiabatic potential at the final height of the barrier and vibrational frequency greater than the ESR frequency.Slovakian Technical Institute and Institute of Geology and Geophysics, Siberian Branch, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 5, pp. 74–77, September–October, 1989.     

Investigations on the compatibility of milk fat fractions and lauric fats

The compatibility of a lauric fat with several milk fat fractions (MF) was investigated. The enthalpy of crystallization was measured by differential scanning calorimetry (DSC). These values were related to the corresponding values calculated for an Ideal Blend. The different compatibility of the milk fat fractions with the lauric fat could be shown by this method very clearly.

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Untersuchungen zur Mischbarkeit/Verträglichkeit von Milchfettfraktionen mit laurischen Fetten

Zusammenfassung Die Mischbarkeit/Verträglichkeit von Milchfettfraktionen mit einem laurischen Fett wurde differenzkalorimetrisch untersucht. Die Auswertung der Befunde bezieht sich auf die entsprechenden Rechnungswerte einer Idealen Mischung. Es wurde nachgewiesen, da sich diese Milchfette deutlich in ihrer Mischbarkeit unterscheiden.

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. $ . , $ - . $ .

     

Catalysts for metathesis of olefins, prepared by anchoring of MoO2(acac)2 to Al2O3

New highly active catalysts for metathesis of olefins were obtained through the interaction of bis(acetylacetonato)dioxymolybdenum(VI) with surface OH groups of -Al₂O₃ and subsequent reduction in H₂ or CO.

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()(VI) OH -Al₂O₃ H₂ CO .

     

Micellar effect of sodium dodecyl sulfate on the reactions between iron(II) and p-benzoquinone, and iron(III) and hydroquinone

The micellar effet of sodium dodecyl sulfate (SDS) on the initial stages of the reaction between (1) Fe(II) and p-benzoquinone, and (2) Fe(III) and hydroquinone have been investigated. In the former case acceleration was observed, the rate-[surfactant] profile showing a maximum. SDS has an inhibitory effect on the latter reaction. Kinetic analysis has been carried out using Berezin's approach.

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() 1) Fe(II) 2) Fe(III) . - . . , .

     

Mössbauer studies of thermal decomposition of metal(III) hexacyanoferrates(II)

The thermal decomposition of metal(III) hexacyanoferrates(II) (Al, As, Sb, Bi) was studied up to 700° in air by employing Mössbauer, infrared spectroscopy and thermal analysis techniques. With the exception of the bismuth compound, the isomer shift of these hexacyanoferrates(II) increases on dehydration at 200°. Dehydration is complete at 200°, decomposition into the ferrite at 300°, and formation of-Fe₂O₃ from aluminium and bismuth hexacyanoferrates(II) and Fe₃O₄ from antimony and arsenic hexacyanoferrates(II) at 700°.

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Zusammenfassung Die thermische Zersetzung von Metall(III)ferrocyaniden (Al, As, Sb, Bi) wurde bis zu 700° in Luft unter Anwendung der Mössbauer und Infrarotspektroskopie, sowie thermoanalytischer Techniken untersucht. Die Isomerverschiebung dieser Ferrocyanide nimmt mit der Dehydratisierung bei 200° zu, mit Ausnahme des Wismuts. Die Dehydratisierung ist bei 200° abgeschlossen, die Zersetzung zum Ferrit bei 300° und die Bildung von-Fe₂O₃ aus Aluminium- und Wismutferrocyanid, von Fe₃O₄ aus Antimon- und Arsenferrocyanid bei 700°.

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Résumé On a étudié dans l'air jusqu'à 700°, la décomposition thermique des ferrocyanures de métaux trivalents (Al, As, Sb, Bi), par spectroscopies Mössbauer et infrarouge, ainsi que par les techniques d'analyse thermique. Le déplacement des isomères de ces ferrocyanures augmente lors de la déshydratation à 200°, à l'exception du bismuth. La déshydratation est complète à 200°, la décomposition en ferrite à 300°, la formation d'-Fe₂O₃ à partir des ferrocyanures d'aluminium et de bismuth ainsi que du Fe₃O₄ à partir des ferrocyanures de l'antimoine et de l'arsenic à 700°

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-, , — Al, As, Sb, Bi- 700° . , , 200°. 200°, 300° -Fe₂O₃. 700° Fe₃O₄.

     

DTA and TG analysis of heteropolyacids of the series H(3+x)PMo(12−x)VxO40·nH2O

DTA, TG and DTG of molybdovanadophosphoric acids of the series H_(3+x)Mo_(12–x)V_xO₄₀· nH₂O (x=0, 1, 2, 3) were carried out. The samples with the highest content of water of crystallization (n=19–34) fuse above 40 °C, giving solutions of heteropolyacids which boil at 110 to 130 °C. The total loss of crystallization water occurs below 170–200 °C. The anhydrous acids decompose (dehydroxylation) at temperatures decreasing from the average value of 433 °C forx=0 to about 293 °C forx=3. For these vanadium-containing samples, an exothermic peak not accompanied by weight change appears at about 450, 430 and 390 °C forx=1,2 and 3, respectively, indicating a transformation in the solid state. Ifx=0, a weaker endothermic effect of dehydroxylation overlaps with a stronger exothermic effect, and only one exothermic effect exists, at 435 °C.

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Zusammenfassung An Molybdovanadophosphorsäuren der Formel H_(3+x)Mo_(12–x)V_xO₄₀· H₂O (x=0, 1, 2, 3) wurden DTA-, TG- und DTG-Untersuchungen durchgeführt. Die Proben mit dem größten Kristallwassergehalt (n=19–34) schmelzen oberhalb 40 °C und liefern damit Lösungen von Heteropolysäuren mit einem Siedepunkt zwischen 110 und 130 °C. Der vollständige Verlust des Kristallwassers erfolgt unterhalb 170–200 °C. Die wasserfreien Säuren zersetzen sich (Dehydroxylierung) bei Temperaturen mit einem Durchschnittswert von 433 °C fürx=0 bis herab zu 293 °C fürx=3. Bei diesen vanadiumhaltigen Proben tritt fürx=1, 2 und 3 bei den Temperaturen 450, 430 und 390 °C ein exothermer Peak auf, der von keinem Gewichtsverlust begleitet wird und somit auf eine Strukturänderung des festen Zustandes hinweist. Beix=0 wird ein stärkerer exothermer Effekt von einem schwächeren endothermen überlagert und es existiert bei 435 °C nur ein exothermer Effekt.

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, H_3+xMo_12–xV_xO₄₀·nH₂O, x=, 1, 2, 3. (n=19–34) 40°, 110–130°. ( ) 433° =0 293° =3. , , , 340,430 390° x=1,2,3, , . x=0 , 435°.

     

Zwitterionic [(H3NCH2C≡CC≡CCH2NH3)]Cu2Cl4 π-Complex: Template Synthesis and Crystal Structure

Crystals of the [(H₃NCH₂CCCCCH₂NH₃)]Cu₂Cl₄ -complex, formed in the oxidative dimerization of propargylammonium cations, were obtained by ac electrochemical synthesis from CuCl₂ · 2H₂O and propargylammonium chloride ([CCCH₂NH₃]Cl) and studied by X-ray diffraction analysis (DARCh automated diffractometer, MoK radiation, /2 scan mode; 2275 reflections with F 4(F), R = 0.048). Crystals are monoclinic: space group B2/b, a = 19.591(6) Å, b = 7.299(3) Å, c = 8.636(3) Å, = 106.83(3)°, Z = 4. The structure consists of individual [(H₃NCH₂CCCCCH₂NH₃)]Cu₂Cl₄ moietes united through the elongated Cu···Cl contacts (2.827(5) Å) into chains oriented along the [010] direction. The bond of the centrosymmetric propargylammonium dimer is -coordintated by copper(I) atom and is elongated to 1.227(6) Å.     

Décomposition thermique du sulfite de fer(II) anhydre

Résumé Sous azote ou sous vide, le sulfite ferreux anhydre se décompose vers 210° en magnétite, pyrite et dioxyde de soufre. Concurremment une réaction de dismutation intervient avec formation de FeSO₄, Fe₃O₄ et FeS₂. Lorsque la température atteint 320°, la pyrite et le sulfate réagissent ensemble pour donner Fe_1–xS, Fe₃O₄ et SO₂. Au-delà de 370° le sulfure ferreux non-stchiométrique commence à réagir à son tour avec le sulfate restant pour former de la magnetite et du dioxyde de soufre.

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In nitrogen or under vacuum, anhydrous iron(II) sulfite decomposes near 210° to magnetite, pyrite and sulfur dioxide. A parallel disproportionation reaction occurs with formation of FeSO₄, Fe₃O₄ and FeS₂. When the temperature reaches 320°, pyrite and sulfate react together to give Fe_1–xS, Fe₃O₄ and SO₂. Above 370° the non-stoichiometric ferrous sulfide begins to react with the remaining sulfate to give magnetite and sulfur dioxide.

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Zusammenfassung Unter Stickstoff oder im Vakuum zersetzt sich das wasserfreie Eisen(II)-sulfit in der Nähe von 210 °C zu Magnetit, Pyrit und Schwefeldioxid. Parallel hierzu findet eine Disproportionierung unter Bildung von FeSO₄, Fe₃O₄ und FeS₂ statt. Wenn die Temperatur 320 °C erreicht, reagieren Pyrit und Sulfat unter Bildung von Fe_1–xS, Fe₃O₄ und SO₂ Oberhalb von 370 °C beginnt das nichtstöchiometrische Eisensulfit seinerseits mit dem restlichen Sulfat zu reagieren um Magnetit und Schwefeldioxid zu ergeben.

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(II) 210° , . FeSO₄, Fe₃O₄ FeS₂. 320°, , Fe_1–xS, Fe₃O₄ SO₂. 370° .

     

Synthesis and physico-chemical and biological studies on ruthenium (III) complexes with Schiff bases derived from aminocarboxylic acids

Summary Ruthenium(III) complexes of types [Ru(L)₃], [Ru(L)Cl(H₂O)₂], [Ru(L)Cl₂]_n, [Ru(L)Cl(H₂O)]_n(LH =Schiff bases derived from anthranilic acid and benzaldehyde, acetophenone, vanillin, cinnamaldehyde orm-hydroxyacetophenone; LH₂=Schiff bases derived from anthranilic acid and salicylaldehyde oro-hydroxyacetophenone; LH=Schiff bases derived fromp-aminobenzoic acid and benzaldehyde, acetophenone, vanillin, cinnamaldehyde orm-hydroxyacetophenone; LH₂=Schiff bases derived fromp-aminobenzoic acid and salicylaldehyde oro-hydroxyacetophenone) have been synthesized and characterized on the basis of elemental analyses, conductance, magnetic moment and spectral (electronic, i.r. and¹H n.m.r.) data. The wavelengths of the principal electronic absorption peaks have been accounted for quantitatively in terms of crystal field theory and various parameters have been evaluated. On the basis of the electronic spectra, an octahedral geometry has been established for all these complexes except [Ru(L)Cl₂]_n. The complexes [Ru(L)Cl₂]_n are pentacoordinate and a trigonal-bipyramidal environment, D_3h, is suggested for the ruthenium(III) ion. The thermal behaviour of these complexes has also been studied by t.g., d.t.g and d.s.c techniques. Heats of reaction for the decomposition steps were calculated from the d.s.c. curves. The antifungal and antiviral activities of the complexes with Schiff bases derived from anthranilic acid were also investigated.     

Mechanism of non-catalytic proton exchange in aprotic low-polar solvents

The kinetics of proton exchange for the CD₃OH–(CH₃)₃COH and CD₃OH–CH₃COOH systems in various solvents have been studied by dynamic¹H and²H NMR. The mechanism of the process is discussed.

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¹H ²H CD₃OH–(CH₃)₃COH CD₃OH–CH₃COOH . .

     

Thermal and some other properties of the complexes crystallizing from the system Ni(II)-en-[Ni(CN)4]2−-H2O

Seven complex compounds exhibiting the compositions Ni(en)₃Ni(CN)₄·H₂O (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄·2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2.5H₂O (VI) and-Ni(en)₂Ni(CN)₄ (VII) were prepared from the system Ni-en-[Ni(CN)₄]^2–-H₂O. These compounds were examined by the methods of infrared spectroscopy, X-ray powder diffractometry, UV-VIS reflectance spectroscopy, and also by the measurement of magnetic moments. The thermal stability, the stoichiometry of thermal decomposition and the mutual transformations were investigated with a derivatograph. The reactions proceeding according to the following schemes were observed if the system was heated to appropriate temperature: (I)(II)(III)(V)(IV) and (VI)(VII)(III)(V)(IV) Process (VII)(III) represents isomerization. The reversibility of the process (V)(IV) is due to the high hygroscopicity of the anhydrous complex. The changes in structure in the course of the individual processes are discussed.

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Zusammenfassung Aus einem System Ni-en-[Ni(CN)₄]^2–-H₂O wurden sieben Komplexe der Formeln Ni(en)₃Ni(CN)₄·H₂O (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄·2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2.5H₂O (VI) und-Ni(en)₂Ni(CN)₄ (VII) hergestellt. Diese Verbindungen wurden mittels IR-Spektroskopie, Röntgenpulverdiffraktometrie, UV-Reflexionsspektroskopie und durch Messungen des magnetischen Momentes untersucht. Die Wärmestabilität, die Stöchiometrie des thermischen Zerfalles und die gegenseitigen Umwandlungen wurden mittels eines Derivatographen untersucht. Wird das System auf geeignete Temperaturen erhitzt, kann der Reaktionsverlauf durch folgendes Schema dargestellt werden: (I)(II)(III)(V)(IV) und (VI)(VII)(III)(V)(IV).Der Prozeß (VII)(III) verkörpert eine Isomerisierung. Die Umkehrbarkeit von Prozeß (V)(IV) ist auf die ausgeprägten Hygroskopieeigenschaften des wasserfreien Komplexes zurückzuführen. Es werden die im Ablaufe der einzelnen Prozesse vorgehenden Strukturveränderungen besprochen.

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Ni- -[No(N)]² -₂ Ni(en)₃Ni(CN)₄ · ₂ (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄-2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2,5H₂O (VI) -Ni(en)₂Ni(CN)₄ (VII). , , - , . , . (I)(II)(III)(V)(IV) (VI)(VII)(III)(V)(IV). (VII)(III) . (V)(IV) . .

     

Heterogeneous reactions of solid nickel(II) complexes XXIII

The thermal decompositions of the following compounds were studied: Ni(NCO)₂(3-Etpy)₄. (I), Ni(NCO)₂(3-Clpy)₄ (II), Ni(NCO)₂(3-Brpy)₄ (III), Ni(NCO)₂(3-NH₂py)₄ (IV), Ni(NCO)₂(3-Clpy)₂·2H₂O (V) and Ni(NCO)₂(3-Brpy)₂·2H₂O (VI). The release of volatile ligands (3-Rpy and H₂O) is a two-step process, Ni(NCO)₂(3-Etpy)₂ (VII), Ni(NCO)₂(3-Clpy)₂ (VIII), Ni(NCO)₂(3-Brpy)₂ (IX) and Ni(NCO)₂(3-NH₂py)₂ (X) being formed as intermediate complexes. The loss of the last molecules of volatile 3-Rpy ligands is accompanied by NCO ligand decomposition. The spectral and magnetic data indicated pseudooctahedral configuration for all complexes I-X.

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Zusammenfassung Die thermische Zersetzung der folgenden Verbindungen wurde untersucht: Ni(NCO)₂(3-Etpy)₄ (I), Ni(NCO)₂(3-Clpy)₄ (II), Ni(NCO)₂(3-Brpy)₄ (III), Ni(NCO)₂(3-NH₂py)₄ (IV), Ni(NCO)₂(3-Clpy)₂·2H₂O (V) und Ni(NCO)₂(3-Brpy)₂·2H₂O (VI). Die flüchtigen Liganden (3-Rpy und H₂O) werden in zwei Schritten abgegeben, wobei Ni(NCO)₂(3-Etpy)₂ (VII), Ni(NCO)₂(3-Clpy)₂ (VIII), Ni(NCO)₂(3-Brpy)₂ (IX) und Ni(NCO)₂(3-NH₂py)₂ (X) als intermediäre Komplexe gebildet werden. Die Abgabe der letzten Moleküle der flüchtigen 3-Rpy-Liganden geht mit der Zersetzung des NCO-Liganden einher. Die spektrometrischen und magnetischen Daten weisen auf eine pseudooktaedrische Konfiguration aller Komplexe (I-X) hin.

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: Ni(NCO)₂(3-Etpy)₄ (I), Ni(NCO)₂(3-Clpy)₄ (II), Ni(NCO)₂(3-Brpy)₄ (III), Ni(NCO)₂(3-NH₂py)₄ (IV), Ni(NCO)₂(3Clpy)₂·2H₂O(V) Ni(NCO)₂(3-Brpy)₂·2H₂O (VI). (3-Rpy H₂O) , Ni(NCO)₂(3-Etpy)₂ (VII), Ni(NCO)₂(3-Clpy)₂ (VIII), Ni(NCO)₂(3-Brpy)₂ (IX) Ni(NCO)₂(3NH₂py)₂ (X). . .