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 . .

     

ESR studies of the generation of adsorbed oxygen radicals under irradiation of CaO in the range of surface absorption

Anion-radicals of oxygen O ₂ ^– and complexes of molecular oxygen with hole centers [X·O₂] (g₁=2.002, g₂=2.009, g ₃ ¹ =2–015, g ₃ ² =2.016) and [Y·O₂] (g=2.004, g=2.012) have been found to form under CaO irradiation in the range of surface absorption (h4 eV). ESR spectra of X and Y centers have not been observed. They are suggested to be anion-radicals O _st ^– in various coordinations: (O _3C ^– )_st and (O _4C ^– )_st, respectively.

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- O ₂ ^– [XO₂] (g₁=2.002, g₂=2.009, g ₃ ¹ =2.015, g ₃ ² =2.016) (g=2.004, g=2.012) CaO (h4 ). X Y . , - O _st ^– , : (O _3C ^– )_st (O _4C ^– )_st, .

     

Molecular isotope exchange of14CO in surface carbonyl complexes of rhodium

Molecular isotope exchange of CO with¹⁴CO for Rh₆(CO)₁₆/Sn(II)–SiO₂, Rh₆(CO)₁₆/Al₂O₃, Rh(I)(CO)₂/Al₂O₃, Rh₄(CO)₁₂/Al₂O₃ carbonyl complexes of rhodium has been studied. Estimates of the activation energies and a mechanism of the CO exchange are suggested.

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, (Rh₆(CO)₁₆/Sn(II)–SiO₂, Rh₆(CO)₁₆/Al₂O₃, Rh^I(CO)₂/Al₂O₃, Rh₄(CO)₁₂/Al₂O₃), ¹⁴CO. CO .

     

Reactivity of coordinated O2? towards. One-electron oxidants

Ion-radical complexes Ti(IV) (O ₂ ^– ) are unreactive towards most oxidants except Ce(IV) and Cr₂O ₇ ^2– . The one-electron redox potential for the O_{2 coord.}/O _{2 coord.} ^– couple lies between 1 and 1.6 V.

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- O ₂ ^– Ti(IV) , Ce(IV) Cr₂ O ₇ ^2– . - O_{2 .}/O ₂ ^– . 1 1,6 .

     

Influence of substituents on rate constants for recombination of tertiary peroxy radicals

A linear correlation between the logarithm of rate constant (2k_t) for recombination of tertiary peroxy radicals (ROO)^* and ^* constants of substituents R was found to be 1g 2k_t=lg 2k _t ^° . The calculated values are 1g 2k _t ^° =4.59±0.08 and ^*=5.56±0.35.

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I (2k_t) (ROO) R: 1g 2k_t=lg 2k _t ^° . , 1g 1g 2k _t ^° =4,59±0,08 =5,56±0,35

     

Eigenschaften und Zustandsdiagramme einiger silberchalkogenidsysteme

Zusammenfassung Auf Grund einer von uns durchgeführten Untersuchung über die Zustandsdiagramme der Silberchalkogenidsysteme Ag₂Te-Ag₂Se, Ag₂Te-Ag₂S, Ag₂Se-Ag₂S und über die Diagonalquerschnitte Ag₂Se_0.5Te_0.5-Ag₂S, Ag₂S_0.5Te_0.5-Ag₂Se, Ag₂Se_0.5S_0.5-Ag₂Te wurden ein Projektion des Raumdiagramms der Liquidusflachen und einige der wichtigsten isothermen Schnitte des dreidimensionalen Systems Ag₂Te-Ag₂Se-Ag₂S aufgestellt. Nach der Interpretation der Art und Lage der einzelnen Phasen wurden für jedes der Systeme die elektrischen und wärmephysikalischen Eigenschaften bei Temperaturen von der des flüssigen Stickstoffes bis zu den Temperatures des Phasenübergangs untersucht und der thermoelektrische Wirkungsgrad (Z, K^–1) berechnet.

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On the basis of a previous investigation on the phase diagrams of the silverchalcogenide systems Ag₂Te-Ag₂Se, Ag₂Te-Ag₂S and Ag₂Se-Ag₂S and the diagonal sections Ag₂Se_0.5Te_0.5-Ag₂S, Ag₂S_0.5Te_0.5-Ag₂Se and Ag₂Se_0.5S_0.5-Ag₂Te, the projections of liquidus surfaces and more characteristic isothermal sections of the Ag₂Te-Ag₂Se-Ag₂S phase diagram were constructed. After interpretation of the types and situations of the separate phases in each of the systems studied, their electric and thermophysical properties were investigated in the temperature range from 77 K up to the temperatures of the phase transitions and the values of thermoelectric efficiency were calculated,Z, Ksu–1.

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Ag₂Te-Ag₂Se, Ag₂Te-Ag₂S, Ag₂Se-Ag₂S Ag₂Se_0.50.5-Ag₂S, Ag₂S_0.5Te_0.5-Ag₂Se, Ag₂Se_0.5S_0.5-Ag₂Te Ag₂Te-Ag₂Se-Ag₂S. . 77 . .

     

A new method for preparation of Mo/Al2O3 catalysts for olefin metathesis

A new method of preparation of highly active catalysts for metathesis of -olefins through the anchoring of [Mo₂O₄(C₂O₄)₂(H₂O)₂]^2– anion to the surface of -Al₂O₃ with further thermal activation in H₂ and CO is proposed.

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- [Mo₂O₄(C₂O₄)₂(H₂O₂]^2– -Al₂O₃ H₂ CO.

     

Kinetics of the homogeneous oxidation of hydrogen by platinum(II) and platinum(IV) chloro complexes in aqueous solution

The kinetics of the homogeneous oxidation of hydrogen in the Pt(II)–Pt(IV)–Cl^––H₂O system has been studied for the first time in conditions permitting to avoid the formation of Pt-black. It is shown that platinum (II) [Pt(II)Cl_i(H₂O)_4-i, where i=1, 2, 2], is active in the reaction, whereas the PtCl ₄ ^2– complex and platinum(IV) do not react with hydrogen.

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, Pt-, H₂ Pt^II–Pt^IV–Cl^––H₂O. (II) (Pt^IICl_i(H₂O)_4-i, i=1, 2, 3); PtCl ₄ ^2– (IV) .

     

Influence of substituents on rate constants for recombination of secondary and primary peroxy radicals

A linear correlation has been found between the logarithm of rate constants (2k_t) for the recombination of secondary peroxy radicals (ROO) and the constants of substituents, R:1g 2k_t=(6.84±0.03)+(2.60±0.10) . Rate constant for the recombination of primary peroxy radicals proves to be independent of the substituent nature: 1g 2k_t=8.5±0.4.

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(2k_t) (ROO) R: 1g 2k_t=(6,84±0,03)+(2,60±0,10) . , 1g 2k_t=8,5±0,4.

     

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.     

A new improved expression for gamma-ray detection efficiency of Ge(Li) detectors

In the present paper, a new improved expression for -ray detection efficiency of Ge(Li) detectors, ⁰ , is given. It is represented as a continuous function of x (viz. E ^–1) with a maximum and decreases very rapidly to a small positive value as -ray energy, E, drops to 40 keV or lower, but slowly as E rises to 1.7 MeV or higher. Since it can well represent the whole physical process of the -ray detection, this expression may be one of the simplest and most precise representations, for ⁰ at the present time.     

Exchange of molecular oxygen with the oxygen of an Al2(MoO4)3 catalyst

The kinetics of exchange of¹⁸O-containing molecular oxygen with the oxygen of an Al₂(MoO₄)₃ catalyst has been studied in the temperature range 579–680 °C at Torr. The activation energy of exchange is 57 kcal/mol, and the specific rate of exchange varies between 0.79×10¹¹ and 21.2×10¹¹ molec. cm^–2 sec^–1. Assumptions are made concerning the activity and selectivity of Al₂(MoO₄)₃ with respect to oxidation reactions.

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, O¹⁸, Al₂(MoO₄)₃ 579–680 °C . , 57 /, 0,79·10¹¹ 21,2·10¹¹ O₂/².. Al₂(MoO₄)₃ .

     

Oxidative coupling of methane over Bi2O3?P2O5?K2O/Sm2O3

Oxidative coupling of methane over Bi₂O₃–P₂O₅–K₂O/Sm₂O₃ takes place giving more C₂H₄ as compared to C₂H₆. Sm₂O₃ supported Bi–P–K is a more active and selective catalyst, than TiO₂, -Al₂O₃, SiO₂ and MgO supported catalysts.

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Bi₂O₃–P₂O₅–K₂O/Sm₂O₃ , . Bi–P–K, Sm₂O₃, , TiO₂, -Al₂O₃, SiO₂, MgO.

     

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 - , .

     

Catalytic reactions of hydrocarbon with carbon dioxide over metallic catalysts

The catalytic reaction between hydrocarbons and carbon dioxide, e.g. CH₄+ +CO₂2CO+2H₂ and C₆H₆CH₃+CO₂C₆H₆+2CO+H₂, has been investigated over various metallic catalysts under atmospheric pressure. In general, Rh–Al₂O₃ catalyst was found to be excellent in activity and selectivity. The reaction rates were moderately dependent on the pressure of carbon dioxide, whereas it was little influenced by the pressure of hydrocarbon.

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, ., CH₄+CO₂2CO+2H₂ C₆H₅CH₃+CO₂C₆H₆+2CO+X₂, . , Rh–Al₂O₃ . , .

     

Solvent effect on transformation kinetics of ozone and toluene complex

Medium effect on the decomposition rate of C₆H₅CH₃.O₃ in solvents: n-C₆H₁₄, CHCl₃, CH₂Cl₂, (CH₃)₂CO, CH₃OH and CH₃CN has been studied. Consumption rate of this complex increases in polar solvents.

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C₆H₅CH₃.O₃ n-C₆H₁₄, CHCl₃, CH₂Cl₂, (CH₃)₂CO, CH₃OH, CH₃CN. .

     

Soluble polysaccharides of Rhodotorula flava

Conclusions 1. Xanthalin has been shown to have the structure of 2, 2-dimethyl-3, 4,-diangeloyloxy-3, 4-dihydropyrano-5, 6:6, 7-coumarin on the basis of the preparation of a number of derivatives and cleavage products.2. The following products of the alkaline hydrolysis of xanthalin have been isolated and characterized for the first time: (±)-3, 4-dihydroxy-3, 4-dihydroxanthyletin (isokhellactone), C₁₄H₁₄O₅, with mp 213–215° C and (–)-trans-3-hydroxy-4-methoxy-3, 4-dihydroxanthyletin (isomethylkhellactone, C₁₅H₁₆O₅, with mp 136.5–138° C and [] _D ²⁰ –47.7 (ethanol).Khimiya Prirodnykh Soedinenii, Vol. 6, No. 1, pp. 14–19, 1970     

The electronic spectrum of acrylonitrile

The vapor absorption spectrum of acrylonitrile CH₂CHCN has been measured in the vacuum ultraviolet region. In addition, an all-valence-electron molecular orbital calculation has been used to calculate the electronic structure and spectrum of the molecule. On the basis of the MO calculation, as well as a vibrational analysis of the observed spectrum, several electronic transitions are assigned. The lowest energy absorption band (2107Å, = 150) is assigned as an n ^* transition. Absorption bands at 2030Å (=1600), 1725Å ( = 2100), and 1570Å ( = 1920) are assigned as 0–0 bands associated with transitions that are, respectively, ^*,^*, and ^* in character.

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Zusammenfassung Das UV-Absorptionsspektrum von dampfförmigen Acrylnitril wurde gemessen und eine CNDO/2-Rechnung für die Elektronenstruktur durchgeführt. Auf dieser Basis konnten unter Zuhilfenahme der Analyse der Schwingungsstruktur im beobachteten Spektrum mehrere Banden zugeordnet werden: die 2107-Å-Bande ( = 150) einem n^*-Übergang, die drei Banden bei 2030Å ( = 1600), 1725Å ( = 2100) und 1570 Å ( = 1920)0-0-Übergängen von ^*-, ^*- bzw. ^*-Banden.

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Résumé Mesure du spectre d'absorption en phase vapeur de l'acrilonitrile CH₂CHCN dans la région de l'ultraviolet. Par ailleurs, la structure électronique et le spectre de la molécule ont été calculés à l'aide d'une méthode des orbitales moléculaires semi-empirique pour tous les électrons de valence. Sur cette base, ainsi que sur une analyse vibrationnelle du spectre expérimental, on procède à l'attribution de plusieurs transitions électroniques. La bande d'absorption de plus basse énergie (2107 Å, = 150) est attribuée à une transition n ^*. Les bandes d'absorption à 2030Å ( = 1600), 1275Å ( = 2100) et 1570Å ( = 1920) sont considérées comme des bandes 0 - 0 associées à des transitions ^*, ^* et ^* respectivement.

     

Etude thermoanalytique de conditions de formation du gallate de sodium,II

Résumé L'étude par TG, ATD, analyse chimique et IR du système Na₂O₂/Ga₂O₃ a montré qu'au début du chauffage, sous l'action de la soude, il se formait de l'hydroxogallate qui se transformait en gallate vers 130–150C. Entre 287 et 350, Na₂O₂ et NaOH attaquent conjointement Ga₂O₃. NaGaO₂ obtenu possède des groupements GaO₄. La sensibilité de l'ATD permet de différencier les domaines de réactivité maximale des deux composés sodiques. Audelà de 350, une nouvelle réaction de Na₂O₂ produit principalement du gallate à groupements GaO₆. L'attaque de Ga₂O₃ au cours de ces différentes phases dépend essentiellement de sa variété cristalline.

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Thermogravimetric, differential thermoanalytical and infrared spectroscopic studies of the system Na₂O₂/Ga₂O₃ have shown that in the reaction with sodium hydroxide hydroxogallate is formed, which transforms to gallate in the range of 130 to 150. Between 287 and 350 Na₂O₂ and NaOH attack Ga₂O₃ together, and the NaGaO₂ obtained contains GaO₄ groups. The DTA method permitted to distinguish the ranges of maximum reactivity of the two sodium compounds. Above 350 gallate containing GaO₆ groups is mainly formed in a new reaction of Na₂O₂. The attack of Ga₂O₃ in the course of the different steps depends mainly on its crystal structure.

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Zusammenfassung Thermogravimetrische, differentialthermoanalytische und infrarotspektroskopische Untersuchungen des Systems Na₂O₂/Ga₂O₃ zeigten, daß bei Einwirkung von Natriumhydroxyd Hydroxogallat gebildet wurde, das zwischen 130–150 in Gallat überging. Zwischen 287 und 350 greifen Na₂O₂ und NaOH gemeinsam das Ga₂O₃ an, das erhaltene NaGaO₂ enthält GaO₄ Gruppen. Durch DTA gelang es die Gebiete der maximalen Reaktivität der zwei Natriumverbindungen zu differenzieren. über 350 entsteht durch eine neue Reaktion von Na₂O₂ hauptsächlich Gallat mit GaO₆ Gruppen. Der Aufschluß von Ga₂O₃ hängt während dieser verschiedenen Phasen im wesentlichen von seiner kristallinen Beschaffenheit ab.

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Na₂O₂/Ga₂O₃ , , , 130–150. 287 350 Na₂O₂, NaOH, Ga₂O₃ NaGaO₂ G₄-. . Na₂O₂ 350, , G₆-. G₂₃ .