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941.
The reductions of several substituted acetophenones using supercritical 2-propanol were carried out to estimate the Hammett's reaction constant (ρ=0.33). Also, the reduction of acetophenone using supercritical deuteriated 2-propanol was carried out to determine the rate-determining step. The kinetic isotope effects were observed in the reduction using 2-deuterio-2-propanol (kH/kD=1.6) and O-deuterio-2-propanol (kH/kD=2.0). These findings suggest that the reaction proceeds via a cyclic transition state between acetophenone and 2-propanol similar to that of the Meerwein-Ponndorf-Verley reduction. 相似文献
942.
Susumu Narita Takeshi Hamakawa Tetsuo Morikawa Tai-ichi Shibuya 《Monatshefte für Chemie / Chemical Monthly》2002,133(7):987-990
Summary. The generalized Pauling bond order was enumerated in the C60 fullerene cage molecule (truncated icosahedral symmetry). This index measures chemical similarity in fullerene derivatives
such as dihydrofullerene (C60H2), anionized monohydrofullerene (C60H−), N-substituted monohydrofullerene (C59NH), the fullerene dimer ((C60)2), and the dianionic fullerene dimer ((C60)2
2−). It is also useful in judging the chemical stability of isomers.
Received October 9, 2001. Accepted November 9, 2001 相似文献
943.
Malhotra E. Kaushik N. K. Sodhi G. S. 《Journal of Thermal Analysis and Calorimetry》2002,68(1):215-222
A number of ionic chelate complexes of maltol(A) and hafnium(IV) the type[(η5−C5H5)2HfL]+[MCl3]− (B) [HL=maltol; M=Zn(II), Cd(II), Hg(II), Cu(II)]have been synthesized and characterized by spectral studies (IR, UV, 1H NMR and 13C NMR). The stoichiometry of the complexes has been confirmed by conductance measurements. Thermogravimetric (TG) and differential
thermal analytical (DTA) studies have been carried out for these complexes and from TG curves, the order, apparent activation
energy and apparent activation entropy of the thermal decomposition reactions have been elucidated .The order in each case
has been determined to be one and the degree of spontaneity and lability have been inferred from the apparent activation energy
and entropy, respectively. Thermal parameters have been correlated with some structural aspects of the complexes concerned.
From differential thermal analysis curves, the heat of reaction has been calculated.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
944.
Density of supercritical CO_2-tetrahydrofuran binary mixture and the partial molar volume of the cosolvent 总被引:1,自引:0,他引:1
The densities of supercritical CO2-tetrahydrofuran (cosolvent) binary mixture weremeasured at temperatures in range of 308.15 to 323.15 K and at pressure up to 16.5 MPa.The concentrations of tetrahydrofuran were from 0 to 0.57 mol/L.The partial molar volume of tetrahydrofuran was calculated based on the relationship between the density of the mixture and the concentration of the cosolvent.It is observed that the partial molar volume of the cosolvent is negative and the absolute value decreases with increasing pressure and the concentration of the cosolvent. 相似文献
945.
Changeable size moving window partial least squares (CSMWPLS) and searching combination moving window partial least squares (SCMWPLS) are proposed to search for an optimized spectral interval and an optimized combination of spectral regions from informative regions obtained by a previously proposed spectral interval selection method, moving window partial least squares (MWPLSR) [Anal. Chem. 74 (2002) 3555]. The utilization of informative regions aims to construct better PLS models than those based on the whole spectral points. The purpose of CSMWPLS and SCMWPLS is to optimize the informative regions and their combination to further improve the prediction ability of the PLS models. The results of their application to an open-path (OP)/FT-IR spectra data set show that the proposed methods, especially SCMWPLS can find out an optimized combination, with which one can improve, often significantly, the performance of the corresponding PLS model, in terms of low prediction error, root mean square error of prediction (RMSEP) with the reasonable latent variable (LVs) number, comparing with the results obtained using whole spectra or direct combination of informative regions for a compound. Regions consisting of the combinations obtained can easily be explained by the existence of IR absorption bands in those spectral regions. 相似文献
946.
A nickel catalyst was nodeled with ligand L^2,[NH=CH-CH=CH-0]^-,which should have potential use as a syndiotactic plyolefin catalyst,and the reaction mechanism was studied by theoretical calculations using the density functinal method at the B3LYP/LANL2MB level.The mechanism involves the formation of the intermediate [NiL^2Me]^ ,in which the metal occupies a T-shaped geometry.This intermediate has two possible structures with the methyl group trans either to the oxygen or to the nitrogen atom of L^2.The results show that both structures can lead to the desired product via similar reaction paths,A and B.Thus,the polymerization could be considered as taking place either with the alkyl group occupying the position trans to the Ni-0 or trans to the Ni-N bond in the catalyst.The polymerization process thus favors the catalysis of syndiotactic polyolefins.The syndiotactic synthesis effects could also be enhanced by varations in the ligand substituents.From energy considerations,we can conclude that it is more favorable for the methyl ttrans-O position to form a complex than to occupy the trans-N position.From bond length considerations,it is also more favoured for ethene to occupy the trans-O position than to occupy the trans-N position. 相似文献
947.
W. Kunz J. Barthel L. Klein T. Cartailler P. Turq B. Reindl 《Journal of solution chemistry》1991,20(9):875-891
A variety of methods has been used for the study of lithium bromide solutions in acetonitrile yielding by their combination reliable information on different levels of approximation. Osmotic coefficients based on precise vapor pressure measurements are reproduced by CM (chemical model) and HNC (hypernetted chain) calculations and by BD (brownian dynamics) simulations. The results of neutron scattering experiments are treated with the help of HNC and BD methods. Hartree-Fock calculations on isolated LiBr pairs and solvated lithium ions yield reliable particle distances and reveal the geometry of the lithium solvation sphere. 相似文献
948.
疏水分配常数用于反相液相色谱保留值的预测 总被引:2,自引:0,他引:2
在反相液相色谱保留值基本方程log k_′=a+_cC_B的基础上,描述了采用疏水分配常数及氢键作用能来预测a、c参数的方法,并系统讨论了疏水分配常数对参数a、c的影响,借此对反相液相色谱宽浓度范围内的保留值进行了预测。 相似文献
949.
We present a systematic procedure for the optimization of the expansion basis for the limited expansion of diatomic overlap density functional theory (LEDO-DFT) and report on optimized auxiliary orbitals for the Ahlrichs split valence plus polarization basis set (SVP) for the elements H, Li--F, and Na--Cl. A new method to deal with near-linear dependences in the LEDO expansion basis is introduced, which greatly reduces the computational effort of LEDO-DFT calculations. Numerical results for a test set of small molecules demonstrate the accuracy of electronic energies, structural parameters, dipole moments, and harmonic frequencies. For larger molecular systems the numerical errors introduced by the LEDO approximation can lead to an uncontrollable behavior of the self-consistent field (SCF) process. A projection technique suggested by L?wdin is presented in the framework of LEDO-DFT, which guarantees for SCF convergence. Numerical results on some critical test molecules suggest the general applicability of the auxiliary orbitals presented in combination with this projection technique. Timing results indicate that LEDO-DFT is competitive with conventional density fitting methods. 相似文献
950.
Sandrine Bouquillon Ulla Létinois-Halbes Jacques Muzart 《Journal of organometallic chemistry》2003,687(2):377-383
The reaction between palladium acetate, (−)-ephedrine and potassium acetate led to bis-chelate complex Pd[OCH(Ph)NH(Me)]2 whose the trans-structure is obtained from calculations. The use of this complex to catalyze either the 1,4-hydrogenation of (E)-2-benzyliden-1-tetralone or Heck reaction of phenyl iodide with 3-methyl-3-buten-2-ol led to a low enantiomeric excess. 相似文献