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11.
Ion-molecule reactions between the O=P(OCH(3))(2) (+) phosphonium ions and five aliphatic esters (methyl acetate, methyl propionate, methyl 2-methylpropionate, methyl butyrate and ethyl acetate) were performed in a quadrupole ion trap mass spectrometer. The O=P(OCH(3))(2) (+) phosphonium ions, formed by electron ionization from neutral trimethyl phosphite, were found to react with aliphatic esters to give an adduct ion [RR'CHCOOR", O=P(OCH(3))(2)](+), which loses spontaneously a molecule of ketene CH(2)=CO or substituted ketenes RR'C=CO. Isotope-labeled methyl acetate was used to elucidate fragmentation mechanisms. The potential energy surface obtained from B3LYP/6-31G(d,p) calculations for the reaction between O=P(OCH(3))(2) (+) and methyl acetate is described. 相似文献
12.
Jean-Claude Leclerc 《International journal of quantum chemistry》1976,10(5):781-789
Introduction of noninteger powers of r (or the elliptical coordinate ξ) in the definition of the 1s AO is shown to give better approximate wave-functions for the ground states of H2 and He than other functions of comparable complexity. This trend is examined for various definitions of hybrid Slater–Gaussian orbitals using a limited CI . The best optimized single-term expansion energy is only 0.000160 a.u. above the “SCF limit” for H2 at R = 1.4 a.u. and 0.000382 a.u. for He at R = 1.3 a.u. 相似文献
13.
14.
Dr. Sébastien Lemouzy Florian Cuminet Dimitri Berne Dr. Sylvain Caillol Dr. Vincent Ladmiral Prof. Rinaldo Poli Dr. Eric Leclerc 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(48):e202201135
Vitrimers are a third class of polymers gathering the mechanical properties and solvent resistance of 3D thermosets and the reprocessability of thermoplastics. This unique behaviour is due to the triggering of certain covalent exchange reactions that allow the network to rearrange upon application of a stimulus. The constitutive feature of vitrimers is the adoption of a glass-like viscosity during the rearrangement of the network, often due to an associative mechanism for the exchange reaction. Transesterification networks are one of the most studied type of vitrimers that usually require the incorporation of a catalyst, implying the associated drawbacks. Following up on a recent report on catalyst-free transesterification vitrimers in which the ester functions are particularly reactive thanks to the presence of fluorine atoms in α- or β-position, parallel DFT calculations and an experimental kinetic study on model molecules are presented in order to quantitatively assess the effect of neighbouring fluorinated groups on the transesterification reaction rate. 相似文献
15.
M. H. Hakka H. Bennadji J. Biet M. Yahyaoui B. Sirjean V. Warth L. Coniglio O. Herbinet P. A. Glaude F. Billaud F. Battin‐Leclerc 《国际化学动力学杂志》2010,42(4):226-252
This paper describes an experimental and modeling study of the oxidation of methyl and ethyl butanoates in a shock tube. The ignition delays of these two esters mixed with oxygen and argon for equivalence ratios from 0.25 to 2 and ester concentrations of 0.5% and 1% were measured behind a reflected shock wave for temperatures from 1250 to 2000 K and pressures around 8 atm. To extend the range of studied temperatures in the case of methyl butanoate, two sets of measurements were also made in a jet‐stirred reactor at 800 and 850 K, at atmospheric pressure, at residence times varying between 1.5 and 9 s and for equivalence ratios of 0.5 and 1. Detailed mechanisms for the combustion of methyl and ethyl butanoates have been automatically generated using a version of EXGAS software improved to take into account these oxygenated reactants. These mechanisms have been validated through comparison of simulated and experimental results in both types of reactor. The main reaction pathways have been derived from reaction flux and sensitivity analyses performed at different temperatures. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 226–252, 2010 相似文献
16.
High-throughput approaches for the discovery and optimization of new olefin polymerization catalysts
Murphy V Bei X Boussie TR Brümmer O Diamond GM Goh C Hall KA Lapointe AM Leclerc M Longmire JM Shoemaker JA Turner H Weinberg WH 《Chemical record (New York, N.Y.)》2002,2(4):278-289
The discovery of new olefin polymerization catalysts is currently a time-intensive trial-and-error process with no guarantee of success. A fully integrated high-throughput screening workflow for the discovery of new catalysts for polyolefin production has been implemented at Symyx Technologies. The workflow includes the design of the metal-ligand libraries using custom-made computer software, automated delivery of metal precursors and ligands into the reactors using a liquid-handling robot, and a rapid primary screen that serves to assess the potential of each metalligand-activator combination as an olefin polymerization catalyst. "Hits" from the primary screen are subjected to secondary screens using a 48-cell parallel polymerization reactor. Individual polymerization reactions are monitored in real time under conditions that provide meaningful information about the performance capabilities of each catalyst. Rapid polymer characterization techniques support the primary and secondary screens. We have discovered many new and interesting catalyst classes using this technology. 相似文献
17.
From a Mössbauer study of an oriented single crystal of Ni0.996S (2% Fe57) at 298 K (above the metal-insulator transition at 230 K) the sign of the quadrupole splitting in Fe57 is determined to be positive; this contrasts with a negative sign found for FeS and Fe0.93S. A tentative model is presented that is consistent with these results and with magnetic anisotropy data. 相似文献
18.
G. Férey A.M. Leclerc R. de Pape J.P. Mariot F. Varret 《Solid State Communications》1979,29(6):477-480
Amorphous FeF3 has been prepared by fast vaporisation of the bulk material and condensation : it has been characterized by X-ray diffraction and differential thermal analysis. Strong antiferromagnetic interactions, but low spin-freezing temperature are observed. The magnetic arrangment is speromagnetic. The spin glass behaviour is questionable; the Mössbauer study reveals an electric field gradient distribution which, in average, has no definite sign. 相似文献
19.
Symmetric and nonsymmetric diindolocarbazoles were successfully synthesized for the first time by a Cadogan ring closure using N-alkyl-2,7-disubstituted carbazole precursors. Cyclization reaction on N-alkyl-2,7-di(2'-nitrophenyl) carbazole derivatives is not regioselective and produced a separable mixture of symmetric and nonsymmetric diindolocarbazoles. A carbazole derivative with methyl protective groups at the 1- and 8-positions was therefore used to obtain a symmetric ladder oligo(p-aniline) (compound 22). Optical and electrochemical properties of compound 22 indicate that its neutral semiconducting form is stable in air. This novel class of electroactive ladder oligomers should create new opportunities in micro- and nanoelectronics. 相似文献
20.
Bernard Leclerc 《Algebras and Representation Theory》2000,3(3):277-287
We obtain some simple relations between decomposition numbers of quantized Schur algebras at an nth root of unity (over a field of characteristic 0). These relations imply that every decomposition number for such an algebra occurs as a decomposition number for some Hecke algebra of type A. We prove similar relations between coefficients of the canonical basis of the q-deformed Fock space representation of
. It follows that these coefficients can all be expressed in terms of those of the global crystal basis of the irreducible subrepresentation generated by the vacuum vector. As a consequence, using the works of Ariki and Varagnolo and Vasserot, it is possible to give a new proof of Lusztig"s character formula for the simple U
v
(sl
r
)-modules at roots of unity, which does not involve representations of
of negative level. 相似文献