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71.
A theoretical study has been undertaken of the relative rates and the regio- and stereo-chemistry of ring closure of a variety of alkenyl, alkenylaryl, alkenylvinyl and similar radicals. The method involves the application of MM2 force-field calculations to model transition structures for which the dimensions of the arrays of reactive centres have been obtained by MNDO-UHF techniques. The results, which generally accord with guidelines based on stereochemical considerations, show excellent qualitative and satisfactory quantitative agreement with experimental data. The method has been successfully applied to complex systems including ring closure of alkylperoxy radicals, and formation of the triquinane system by three consecutive cyclisations. 相似文献
72.
The three main types of hydroxyl groups on a silica surface are classified as isolated, hydrogen bonded, and inaccessible. The isolated and hydrogen bonded groups are the most important as these readily exchange with D(2)O and thus are exposed to reactant molecules. However, it has generally been accepted that the inaccessible groups do not participate in surface reactions as only a small fraction of these groups exchange with D(2)O. It is shown that the inaccessible hydroxyl groups on nonporous fumed silica and mesoporous MCM-48 silica powders and films fully exchange with D(2)O and are reactive with octadecylydimethylchlorosilane when supercritical CO(2) is used as the solvent. Furthermore, it is found that the CO(2) penetrating the regions containing the inaccessible groups is not removed by simple evacuation but rather slowly diffuses from the silica over periods of months. 相似文献
73.
Richard A. Bartsch David A. Babb Bronislaw P. Czech Dhimant H. Desai Eddy Chapoteau Carl R. Gebauer Wolodymyr Zazulak Anad Kumar 《Journal of inclusion phenomena and macrocyclic chemistry》1990,9(2):113-123
Four novel chromogenic benzocryptands and one side-armed chromogenic cryptand have been synthesized and their complexing abilities for alkali metal cations are described. 相似文献
74.
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76.
Ruthenium(II) complexes of monodonor ligands: efficient reagents for asymmetric ketone hydrogenation
Xu YA Clarkson GC Docherty G North CL Woodward G Wills M 《The Journal of organic chemistry》2005,70(20):8079-8087
[Chemical reaction: See text] A series of BINOL-derived ligands have been prepared and incorporated into ruthenium(II) complexes containing a diamine ligand. The complexes have proven to be excellent catalysts for the asymmetric hydrogenation of ketones, giving reduction products with enantiomeric excesses of up to 99%. 相似文献
77.
78.
An investigation to determine the compounds present in the Ln2O3Nb2O5 systems (Ln = La, Gd, and Y) and attempts to activate such compounds with Ti, In, Sb, Bi, Eu, and Tb revealed that only the orthoniobate (LnNbO4) compound was a suitable host lattice and LnNbO4:Bi under 2537 Å excitation produced the best phosphors. GdNbO4:Bi is a brighter phosphor than the La and Y analogs, emitting at slightly higher energies. The position of the GdNbO4:Bi peak emission at 4500 Å is independent of the activator concentration whereas peak emissions for LaNbO4:Bi and YNbO4:Bi move to lower energies with increasing Bi concentration. 相似文献
79.
A multisite molecular mechanism for Baeyer-Villiger oxidations on solid catalysts using environmentally friendly H2O2 as oxidant 总被引:1,自引:0,他引:1
Boronat M Corma A Renz M Sastre G Viruela PM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(23):6905-6915
The molecular mechanism of the Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide catalyzed by the Sn-beta zeolite has been investigated by combining molecular mechanics, quantum-chemical calculations, spectroscopic, and kinetic techniques. A theoretical study of the location of Sn in zeolite beta was performed by using atomistic force-field techniques to simulate the local environment of the active site. An interatomic potential for Sn/Si zeolites, which allows the simulation of zeolites containing Sn in a tetrahedral environment, has been developed by fitting it to the experimental properties of quartz and SnO2(rutile). The tin active site has been modeled by means of a Sn(OSiH3)3OH cluster, which includes a defect in the framework that provides the flexibility necessary for the interaction between the adsorbates and the Lewis acid center. Two possible reaction pathways have been considered in the computational study, one of them involving the activation of the cyclohexanone carbonyl group by Sn (1) and the other one involving hydrogen peroxide being activated through the formation of a tin-hydroperoxo intermediate (2). Both the quantum-chemical results and the kinetic study indicate that the reaction follows mechanism 1, and that the catalyst active site consists of two centers: the Lewis acid Sn atom to which cyclohexanone has to coordinate, and the oxygen atom of the Sn-OH group that interacts with H2O2 forming a hydrogen bond. 相似文献