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71.
Sabbe MK Saeys M Reyniers MF Marin GB Van Speybroeck V Waroquier M 《The journal of physical chemistry. A》2005,109(33):7466-7480
A complete and consistent set of 95 Benson group additive values (GAV) for the standard enthalpy of formation of hydrocarbons and hydrocarbon radicals at 298 K and 1 bar is derived from an extensive and accurate database of 233 ab initio standard enthalpies of formation, calculated at the CBS-QB3 level of theory. The accuracy of the database was further improved by adding newly determined bond additive corrections (BAC) to the CBS-QB3 enthalpies. The mean absolute deviation (MAD) for a training set of 51 hydrocarbons is better than 2 kJ mol(-1). GAVs for 16 hydrocarbon groups, i.e., C(C(d))(3)(C), C-(C(d))(4), C-(C(t))(C(d))(C)(2), C-(C(t))(C(d))(2)(C), C-(C(t))(C(d))(3), C-(C(t))(2)(C)(2), C-(C(t))(2)(C(d))(C), C-(C(t))(2)(C(d))(2), C-(C(t))(3)(C), C-(C(t))(3)(C(d)), C-(C(t))(4), C-(C(b))(C(d))(C)(H), C-(C(b))(C(t))(H)(2), C-(C(b))(C(t))(C)(H), C-(C(b))(C(t))(C)(2), C(d)-(C(b))(C(t)), for 25 hydrocarbon radical groups, and several ring strain corrections (RSC) are determined for the first time. The new parameters significantly extend the applicability of Benson's group additivity method. The extensive database allowed an evaluation of previously proposed methods to account for non-next-nearest neighbor interactions (NNI). Here, a novel consistent scheme is proposed to account for NNIs in radicals. In addition, hydrogen bond increments (HBI) are determined for the calculation of radical standard enthalpies of formation. In particular for resonance stabilized radicals, the HBI method provides an improvement over Benson's group additivity method. 相似文献
72.
Denise Baudry Michel Ephritikhine Hugh Felkin Yves Dromzee Yves Jeannin 《Journal of organometallic chemistry》1984,272(3):403-409
Bis(triphenylphosphine)(η-cyclohexa-1,3-diene)rhenium trihydride, (Ph3P)2(η-C6H8)ReH3 (I) crystallises in the space group C2/c with cell dimensions a 22.76(2), b 10.14(1) c 29.813(6) Å, β 97.69(8)°. The final refinement of 126 variables using 1580 non-zero reflections resulted in a final R value of 0.064. In spite of uncertainties in some of the atomic positions, the structure of I is compatible with a trihydrido diene compound with a distorted pentagonal bipyramidal configuration, rather than with a dihydrido cyclohexenyl compound having an “agostic” CH ? Re interaction. The factors which govern the structure of the complexes (Ph3P)2(η-1,3-diene)ReH3 are discussed. 相似文献
73.
The reaction between dibutyltin dilaurate (DBTL) and chloro-4-hexene-2 (containing its isomer chloro-2-hexene-3) as a model compound for the allylic chlorine atom in poly(vinyl chloride) has been studied in dichlorobutane solution at 80°C. The reactions observed—elimination of HCl to give hexadiene and substitution of the laurate group to give hexenyl laurate—are believed to obey E2 and SN2 mechanisms through a common intermediate carbocation, with a rather low selectivity towards the substitution owing to the associated structure of the DBTL. The kinetics are complex because of the complex nature of the exchange reaction between DBTL and Bu2SnCl2. A reverse reaction between the hexenyl laurate and the organo-tin chloride is proposed to explain the limitation of the substitution reaction. 相似文献
74.
The hydrogen-deuterium exchange of H-2 in 4-pyrimidone, a number of 1- and 3-alkyl-4-pyrimidones and several of their thione analogs in deuterium oxide at moderate temperatures is reported. This reaction is apparently not susceptible to acid or base catalysis. Cations of the 4-pyrimidones were found not to exchange H-2 at all in acid media. Catalytic amounts of bases do not alter the exchange rates whereas more concentrated alkali decompose the pyrimidone. However, 1,4(3,4)-dihydro-1,3-dimethyl-4-oxopyrimidinium iodide (and its 6-methyl analog) exchange H-2 quite rapidly in neutral deuterium oxide, almost instantly when triethylamine is added as a catalyst, and very slowly in dilute solutions of deuterium chloride in deuterium oxide. Mechanisms are proposed to account for these phenomena. 相似文献
75.
76.
I. Bauer 《Fresenius' Journal of Analytical Chemistry》1967,231(6):464
Ohne Zusammenfassung 相似文献
77.
Ohne Zusammenfassung7. Mitt.:Hermann Schmid undG. Bauer, Mh. Chem.96, 1508 (1965); dort ältere Mitt. dieser Reihe zitiert. 相似文献
78.
79.
Joël J. E. Moreau Luc Vellutini Catherine Bied Michel Wong Chi Man 《Journal of Sol-Gel Science and Technology》2004,32(1-3):63-67
The acid-hydrolysis of an organo-bridged bisdiethoxysilylated molecular precursor bearing urea groups, (EtO)2MeSi(CH2)3NHCONH(CH2)12NHCONH(CH2)3SiMe(OEt)2, has been performed in pure aqueous medium. Scanning electron microscopy (SEM) analysis of the resulting insoluble solid revealed plate-like forms with a lamellar structure as determined by powder X-ray diffraction (PXRD) studies with a sharp peak at 28.5 Å. The solid state 29Si MAS-NMR spectrum of this bridged siloxane hybrid is consistent with a moderately condensed material with complete preservation of the Si–C bonds throughout the hybrid network. In comparison, the classical sol–gel hydrolysis-condensation of the molecular precursor in ethanol with stoichiometric amount of water and fluoride anion as catalyst produced an amorphous featureless solid. 相似文献
80.
Hae‐Jeong Lee Christopher L. Soles Da‐Wei Liu Barry J. Bauer Wen‐Li Wu 《Journal of Polymer Science.Polymer Physics》2002,40(19):2170-2177
X‐ray reflectivity has been used to determine the mass uptake of probe molecules in porous thin films supported on thick silicon wafers. The adsorption occurs by capillary condensation when the films are exposed to probe vapor at controlled partial vapor pressures. The probe solvent partial pressure was varied by mixing saturated air and dry air at constant temperature or by changing sample temperature at a constant vapor concentration. Pore size distribution in the films can be calculated from the probe uptake with typical porosimetric approaches such as the application of the Kelvin equation to convert partial pressure into pore size. For illustration, the pore size distribution of three different nanoporous thin films, the primary candidate of ultra‐low‐k interlevel dielectrics in the next generation of integrated circuit chips, was determined with this technique. These samples represent different generations of low‐k dielectrics developed by industry. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2170–2177, 2002 相似文献