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11.
Decomposition of N2O has been studied on pure La2CuO4, La2CuO4 with 5 and 10 wt. % LaNi5 and oxidized LaNi5 in the temperature range of 240–490 °C at 50 and 200 Torr initial pressures of N2O. The addition of LaNi5 decreases the energy of activation compared to that of La2CuO4 which has been explained based on the dispersity of NiO over La2CuO4.
N2O La2CuO4 La2CuO4 LaNi5 5–10 .%, 240–490°C N2O 50 200 . LaNi5 , . NiO La2CuO4.相似文献
12.
[reaction: see text] Secondary alpha-lithiosulfinyl carbanions react either intermolecularly, after transmetalation into an organocopper derivative in an S(N)2-type process with zinc carbenoid, or intramolecularly via higher-order zincate to give, through a tandem zinc homologation-beta-elimination reaction the corresponding alkenes. alpha,alpha-Disubstituted alkenes are only formed from tertiary alpha-lithiosulfinyl carbanions via the 1,2-metalate rearrangement. 相似文献
13.
Catalytic decomposition of N2O has been studied over a series of solid solution La2CuxZn1–xO4 (02O, in the temperature range 330–490°C. The observed trends in the kinetics have been explained based on polaron hopping mechanism. Parallel variation between activity and magnetic susceptibility has been observed.
N2O La2CuxZn1–xO4 (0相似文献2O 200 330–490°C. . .
14.
Decomposition of N2O has been studied over La2Cu0.5M0.5O4 (M=Co, Ni, Cu and Zn) between 380 and 485°C at 50 torr initial pressure of N2O to understand the mutual interaction of two different active metal ions of the same concentration and valence in deciding the physico-chemical and catalytic properties. A multicenter type of adsorption of N2O has been visualized and it is found that the rate is governed by the electronic factor.
N2O La2Cu0,5M0,5O4 (M=Co, Ni, Cu Zn) 380–485°C N2O, 50 . , - . N2O. .相似文献
15.
Komath SS Kenoth R Giribabu L Maiya BG Swamy MJ 《Journal of photochemistry and photobiology. B, Biology》2000,55(1):49-55
The interaction of several free-base porphyrins and their corresponding copper(II) and zinc(II) derivatives with the galactose-specific lectin from snake gourd (Trichosanthes anguina) seeds has been investigated by absorption and fluorescence spectroscopic techniques. The lectin dimer contains two apparently equivalent binding sites for the porphyrins. Association constants obtained for the interaction of various porphyrins with the lectin are in the range 1.7 x 10(4)-6.2 x 10(5) M(-1), with the metalloporphyrins being seen to have higher affinity for the lectin compared with the free-base analogues. Both positively charged and negatively charged porphyrins bind to snake gourd seed lectin (SGSL) with comparable affinities, suggesting that binding occurs primarily via hydrophobic interactions. Further, binding of porphyrins is found to be largely unaffected by the presence of the sugar ligand, lactose, indicating that the binding sites for the carbohydrate and porphyrin are different. This study thus suggests that the lectin may serve as a receptor for some endogenous non-carbohydrate, hydrophobic ligand in vivo, in addition to the saccharide ligands. It also opens up the possibility of employing the T. anguina lectin in applications such as photodynamic therapy, which involve the use of porphyrins. 相似文献
16.
The reaction of gaseous H2S with aqueous ammonium heptamolybdate in the presence of triethylenetetramine (trien) gave a red complex. The complex was recrystallized in hot water and characterized by element analysis and UV, visible, IR, and 1H NMR spectroscopy. PMR has revealed accidental magnetic equivalence, resulting from the proximity of [MoS4]2- species in one complex molecule to the open triethylenetetramine ligand of another molecule. (TrienH2)[MoS4] crystallizes in the orthorhombic crystal system, space group Pca21, a=13.045(2), b=16.461(3), c=13.754(2) , =90, =90, =90°, V=2953.5(9) 3, Z=8, R1=0.0323, wR2=0.0730. The structure consists of the tetrahedral tetrathiomolybdate anions, forming an extended 3D framework in solids due to the interactions with triene cations via Mo-S...H-N hydrogen bonds. 相似文献
17.
Kumaraswamy S Kommana P Kumar NS Swamy KC 《Chemical communications (Cambridge, England)》2002,(1):40-41
New modes of 1,3-dipolar cycloaddition are uncovered by the isolation of [CH2(6-t-Bu-4-Me-C6H2O)2]P(C(CO2Me)C(CO2Me)N[NP(N3)(OC6H2-6-t-Bu-4-Me)2CH2]N) (3) and [CH2(6-t-Bu-4-Me-C6H2O)2]P(C(CO2Me)C(CO2Me)C(O)N) (4) on treating [CH2(6-t-Bu-4-Me-C6H2O)2]P-X [X = N3 (1) and NCO (2)] with the dipolarophile MeO2CC identical to CCO2Me; compound 4 undergoes an unprecedented ring expansion upon addition of 2-(methylamino)ethanol to afford the spirocycle [CH2(6-t-Bu-4-Me-C6H2O)2]P(OCH2CH2N(Me)CH(CO2Me)CH(CO2Me)C(O)N) (5). 相似文献
18.
The kinetics of oxidation of 2-thiouracil (TU) by sodium N-bromobenzenesulphonamide or bromamine-B (BAB) have been studied in an HCl medium, catalyzed by RuCl3, and in a NaOH media with OsO4 as catalyst, at 313 K. The stoichiometry and oxidation products are the same in both cases, but their kinetic patterns were found to be different. In acid medium the rate shows a first order dependence in each of [BAB] and [TU], and is dependent on [RuIII]. The reaction rate is inversely dependent on [H+]. In alkaline medium, the rate is first order in [BAB] and in [OsVIII] and zero order in [TU]. The reaction rate is dependent on [NaOH]. Activation parameters have been evaluated, solvent isotope effects have been studied in D2O medium, and equilibrium constants were calculated. The activation parameters and rate constants indicate that the catalytic efficiency is: OsVIII > RuIII. The proposed mechanisms and the derived rate laws are consistent with the observed kinetics. 相似文献
19.
K. J. Tony V. Mahadevan J. Rajaram C. S. Swamy 《Reaction Kinetics and Catalysis Letters》1997,62(1):105-116
Thetrans-dioxo ruthenium (VI) complex, [P(C6H5)3C6H5CH2]+[Ru(O)2OAcCl2] or tetrapropylammonium perruthenate catalyzes the oxidation of secondary alcohols to ketones byN-methylmorpholine-N-oxide (NMO). Kinetic studies showed the formation of a complex between catalyst and substrate (alcohol) as the first step
in the mechanism. 相似文献
20.
Manikandan P Muthukumaran R Thomas KR Varghese B Chandramouli GV Manoharan PT 《Inorganic chemistry》2001,40(10):2378-2389
Copper(II) azide complexes of three tridentate ligands namely 2,6-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L), 2,6-(pyrazol-1-ylmethyl)pyridine (L'), and dipropylenetriamine (dpt) yield three kinds of complexes with different azide-binding modes. The ligand L forms two end-on-end (mu-1,3) diazido-bridged binuclear complexes, [CuL(mu-N(3))](2)(ClO(4))(2) (1) and [CuL(mu-N(3))(ClO(4))](2).2CH(3)CN (2), and L' forms a perchlorato-bridged quasi-one-dimensional chain complex, [CuL'(N(3))(ClO(4))](n)() (3) with monodentate azide coordination. The ligation of dipropylenetriamine (dpt) gives a end-on (mu-1,1) diazido-bridged binuclear copper complex [Cu(dpt)(mu-N(3))](2)(ClO(4))(2) (4). The crystal and molecular structures of these complexes have been solved. Variable-temperature EPR results of 1 and 2 are identical and indicate the presence of both ferromagnetic and antiferromagnetic interactions within the dimer, the former dominating at low temperatures and the latter at high temperatures. The unusual temperature-dependent magnetic moment and EPR spectra of this dimer reveal the presence of temperature-dependent population of two triplet states, one being caused by antiferromagnetic and the other by ferromagnetic interaction, the former transforming to the latter on cooling. While the interaction of ground spin doublets of the two metal centers gives rise to a ferromagnetic coupling of J(g) = 90.73 cm(-1), the other coupling of J(e) = -185.64 cm(-1) is suggested to be caused by the interaction between an electron in one metal center and an electron from the azide of the other monomer by excitation of a d-electron to the empty ligand orbital. The ferromagnetic state is energetically favored by 104.39 cm(-1). Compound 3 exhibits axial spectra at room temperature and 77 K, and variable-temperature magnetic susceptibility data indicate that the copper centers form a weakly antiferromagnetic one-dimensional chain with J = -0.11 cm(-1). In the case of 4, the unique presence of two nonidentical dimeric units with different bond lengths and bond angles within the unit cell as inferred by crystal structure is proved by single-crystal EPR spectroscopy. 相似文献