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81.
The N-bonded nitrile complexes -[Co(tetren)NCR]3+ (R=Me, Ph, p-MeOC6 H4) have been prepared by the reaction of -[Co(tetren)OH2]3+ with the corresponding nitrile. The kinetics of base hydrolysis have been studied by pH-stat methods. The reactions involve an SN1CB displacement of the nitrile to give the hydroxopentamine; nucleophilic attack at the nitrile carbon to give the corresponding carboxamido complex does not occur. NaN3 reacts with the nitrile complexes in slightly acidic solution (pH ca. 5.7) to give the tetrazolato complexes [Co(tetren)N4 R]2+ (R=Me, Ph) which have been characterised. The reaction of azide ion with -[Co(tetren)NCMe]3+ has been studied kinetically. The reaction is biphasic involving the initial rapid formation of the N1-bonded (5-methyltetrazolato) pentaminecobalt(III) complex with k=2×10–2dm3 mol–1s–1 at 25°C followed by the slow isomerisation to the N2-bonded complex with k=3.5×10–5s–1 at pH 5.7. 相似文献
82.
报道A-β-M'xHy-[GeWOM3(H2O)3O37].nH2O(M=Cr^3^+,Co^2^+,Ni^2^+,Cu^2^+;M'=Bu4N^+,K^+)的立体有择合成法制备及红外和远红外光谱,紫外和可见光谱和循环伏安,磁化率和磁矩,XPS,ESR以及催化活性等研究结果。 相似文献
83.
Xiu-Kui Qu Lan-Ying Zhu Ling Li Xi-Lian Wei Feng Liu De-Zhi Sun 《Journal of solution chemistry》2007,36(5):643-650
As a continuation of our previous investigation, interactions between cyclodextrin (β-CD), γ-cyclodextrin (γ-CD) and alkyl trimethylammonium bromides in aqueous solutions have been studied with titration calorimetry and 1H NMR at 298.15 K. The results are discussed in terms of the amphiphilic interaction of CD with surfactants and the iceberg
structure formed by water molecules existing around the hydrophobic tail of surfactant molecules. The stoichiometry of the β-CD–surfactant system is 1:1 whereas that of the γ-CD–surfactant system is 1:2. The corresponding formation enthalpy (negative) of the complexes of the two systems decreases
with an increase in the number of carbon atoms (n) in hydrophobic chain of surfactant molecule, C
n
H2n+1, whereas the entropy increases with the enlargement of n. 相似文献
84.
Allan C. Baxter James H. Cameron Alexander McAuley Fiona M. McLaren John M. Winfield 《Journal of fluorine chemistry》1977,10(4):289-298
Copper(II) fluorine reacts with the pentafluorides, TaF5, PF5, and AsF5, in acetonitrile to give solvated CuII, hexafluoroanion salts. These react with copper metal to give the corresponding CuI compounds. Similar reactions occur between AsF5 and silver(I) or thallium(I) fluorides, but silver(II) fluoride reacts with MeCN, and AgI hexafluoroarsenate is formed. PF5 oxidises Cu slowly in MeCN to give CuI hexafluorophosphate, but AsF5 has no oxidising ability towards metals in MeCN. Spectroscopic data for Cu(MF6)2·5MeCN and Cu(MF6)·4MeCN (M = Ta or P) are discussed. 相似文献
85.
Changmei Sun Rongjun Qu Qiang Xu Chunnuan Ji Yanzhi Sun 《European Polymer Journal》2007,43(4):1501-1509
Two novel chelating resins were prepared by anchoring ethylenediamine to crosslinked polystyrene via a spacer containing sulfide. Their structures were characterized by Fourier transform-infrared spectra (FTIR) and scanning electron microscopy (SEM). Porous structure parameters of the resins were measured by ASAP 2020 using BET and BJH methods. Their adsorption capacities for several heavy metal ions especially Hg2+ were investigated. The results showed that for the two resins, the more N contents did not mean the better adsorption capacity and the saturated adsorption capacity of poly(2-ethylenediamidomercaptomethylstyrene) (PSM-EDA) for Hg2+ could reach to 3.0 mmol/g at room temperature. Isothermal adsorptions of the resins for Hg2+ could be described by Langmuir formula. The adsorption mechanism of the resins for Hg2+, Cu2+ and Ag+ was confirmed by X-ray photoelectron spectroscopy (XPS) and FTIR. 相似文献
86.
Using an on-line solution-reaction isoperibol calorimeter, the standard molar enthalpies of reaction for the general thermochemical reaction: LnCl3·6H2O(s) + 2C9H7NO(s) + CH3COONa(s) = Ln(C9H6NO)2(C2H3O2)(s) + NaCl(s) + 2HCl(g) + 6H2O(l) (Ln: Nd, Sm), were determined at T=298.15 K, as kJ mol−l, respectively. From the mentioned standard molar enthalpies of reaction and other auxiliary thermodynamic quantities, the standard molar enthalpies of formation of Ln(C9H6NO)2(C2H3O2)(s) (Ln: Nd, Sm), at T=298.15 K, have been derived to be: −(1494.7±3.3) and −(1501.5±3.4) kJ mol−l, respectively. 相似文献
87.
Fu L Wu NQ Yang JH Qu F Johnson DL Kung MC Kung HH Dravid VP 《The journal of physical chemistry. B》2005,109(9):3704-3706
Supported gold catalysts have drawn worldwide interest due to the novel properties and potential applications in industries. However, the origin of the catalytic activity in gold nanoparticles is still not well understood. In this study, time-of-flight secondary ion mass spectroscopy (TOF-SIMS) has been applied to investigate the nature of gold in Au (1.3 wt %)/gamma-Al2O3 and Au (2.8 wt %)/TiO2 catalysts prepared by the deposition-precipitation method. The SIMS spectrum of the supported gold catalysts presented AuO-, AuO2-, and AuOH- ion clusters. These measurements show direct evidence for oxidized gold on supported gold catalysts and may be helpful to gaining better understanding of the origin of the catalytic activity. 相似文献
88.
Z. H. Zhang Z. J. Ku H. R. Li Y. Liu S. S. Qu 《Journal of Thermal Analysis and Calorimetry》2005,79(1):169-173
The solid-state ternary complex of terbium chloride with L-tyrosine and glycine, [Tb(Tyr)(Gly)3Cl3·3H2O], was synthesized and characterized. Using a solution-reaction isoperibol calorimeter, the enthalpy of reaction for the following reaction, TbCl3·6H2O(s)+Tyr(s)+3Gly(s)=Tb(Tyr)(Gly)3Cl3·3H2O(s)+3H2O(l), was determined to be (5.1±0.6) kJ mol-1. The standard enthalpy of formation of Tb(Tyr)(Gly)3Cl3-3H2O at T=298.15 K has been derived as -(4267.3±2.3) kJ mol-1. The thermal decomposition kinetics of the complex was studied by non-isothermal thermogravimetry in the temperature range of 325-675 K. Two main mass loss stages existed in the process of the decomposition of the complex, the kinetic parameters for the second stage were analyzed by means of differential and integral methods, respectively. Comparing the results of differential and integral methods, mechanism functions of the thermal decomposition reaction for its second stage were proposed. The kinetic equation can be expressed as: d/dt=Aexp(-E/RT)(1-)2. The average values of the apparent activation energy E and pre-exponential factor A were 213.18 kJ mol-1 and 2.51·1020 s-1, respectively. 相似文献
89.
Ethylene tetramerization: a new route to produce 1-octene in exceptionally high selectivities 总被引:11,自引:0,他引:11
Bollmann A Blann K Dixon JT Hess FM Killian E Maumela H McGuinness DS Morgan DH Neveling A Otto S Overett M Slawin AM Wasserscheid P Kuhlmann S 《Journal of the American Chemical Society》2004,126(45):14712-14713
Linear alpha-olefins, such as 1-hexene and 1-octene, are important comonomers in the production of linear low-density polyethylene (LLDPE). The conventional method of producing 1-hexene and 1-octene is by oligomerization of ethylene, which yields a wide spectrum of linear alpha-olefins (LAOs). While there exists several processes for producing 1-hexene via ethylene trimerization, a similar route for the selective production of 1-octene has so far been elusive. We now, for the first time, report an unprecedented ethylene tetramerization reaction that produces 1-octene in selectivities exceeding 70%, using an aluminoxane-activated chromium/((R2)2P)2NR1 catalyst system. 相似文献
90.
Yu H. G. Yu Dong J. X. Qin C. Q. Liu Y. Qu S. S. 《Journal of Thermal Analysis and Calorimetry》2004,75(3):807-813
The energy of combustion of crystalline 3,4,5-trimethoxybenzoic acid in oxygen at T=298.15 K was determined to be -4795.9±1.3 kJ mol-1 using combustion calorimetry. The derived standard molar enthalpies of formation of 3,4,5-trimethoxybenzoic acid in crystalline
and gaseous states at T=298.15 K, ΔfHm
Θ (cr) and ΔfHm
Θ (g), were -852.9±1.9 and -721.7±2.0 kJ mol-1, respectively. The reliability of the results obtained was commented upon and compared with literature values.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献