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951.
Appelhans LN Zuccaccia D Kovacevic A Chianese AR Miecznikowski JR Macchioni A Clot E Eisenstein O Crabtree RH 《Journal of the American Chemical Society》2005,127(46):16299-16311
Changing the counteranion along the series Br, BF4, PF6, SbF6 in their ion-paired 2-pyridylmethyl imidazolium salts causes the kinetic reaction products with IrH5(PPh3)2 to switch from chelating N-heterocyclic carbenes (NHCs) having normal C2 (N path) to abnormal C5 binding (AN path). Computational work (DFT) suggests that the AN path involves C-H oxidative addition to Ir(III) to give Ir(V) with little anion dependence. The N path, in contrast, goes by heterolytic C-H activation with proton transfer to the adjacent hydride. The proton that is transferred is accompanied by the counteranion in an anion-coupled proton transfer, leading to an anion dependence of the N path, and therefore of the N/AN selectivity. The N path goes via Ir(III), not Ir(V), because the normal NHC is a much less strong donor ligand than the abnormal NHC. PGSE NMR experiments support the formation of ion-pair in both the reactants and the products. 19F,1H-HOESY NMR experiments indicate an ion-pair structure for the products that is consistent with the computational prediction (ONIOM(B3PW91/UFF)). 相似文献
952.
Yin G Buchalova M Danby AM Perkins CM Kitko D Carter JD Scheper WM Busch DH 《Journal of the American Chemical Society》2005,127(49):17170-17171
The reactive intermediates and mechanisms of oxygenation of olefins by manganese complexes were investigated by treating olefins with newly synthesized [MnIV(Me2EBC)(OH)2](PF6)2 in the presence and absence of peroxide and by studying its catalytic epoxidation reaction in normal aqueous solution and, individually, with isotopically labeled H218O, 18O2, and H218O2. The manganese oxo species is not the reactive intermediate for the oxygen transfer process mediated by this manganese complex. A novel manganese(IV) peroxide intermediate, MnIV(Me2EBC)(O)(OOH)+, was captured by mass spectrometry and is proposed as the intermediate that oxygenates olefins in this catalytic system. 相似文献
953.
A number of aryl isocyanates were adducted to 1,2-diazabicyclo[2.2.2]octane and afforded 2-phenyl-carbamoyl-1,2-diazabicyclo[2.2.2]octanes. Some of the products displayed anticonvulsant activity. 相似文献
954.
An efficient approach to the total synthesis of the marine derived polypropionate cyercene A is described. A key feature of the synthesis is the development of methodology for the diastereoselective Wadsworth-Emmons type condensation of a functionalised γ-pyrone unit. 相似文献
955.
Nitropyridines reacted with an excess of vinyl Grignard reagent to produce 4- or 6-azaindoles. Improved yields were obtained when a halogen atom was present at the position alpha to the nitrogen atom in the pyridine ring. 相似文献
956.
Multicomponent adsorption data of a fermentation broth containing adipoyl-7-amino-3-deacetoxycephalosporanic acid (adipoyl-7-ADCA), a cephalosporin precursor for 7-ADCA, and two key impurities, alpha-hydroxyadipoyl-7-ADCA and alpha-aminoadipoyl-7-ADCA were obtained from batch equilibrium and frontal chromatography tests. Amberlite XAD-1600 was chosen as the resin. A rate model was applied to simulate the chromatograms. An alkaline buffer, which by itself has no affinity for the resin, was used as the eluent. The widely used reversed-phase modulator model is inaccurate in explaining the stepwise elution data. A new model, the induced competition model, has been developed to account for apparent retention of the buffer in the presence of adsorbed species. Close agreement between the simulations and the data was achieved with the new model. 相似文献
957.
含氢硅氧烷的硅氢加成反应 总被引:2,自引:0,他引:2
含氢硅氧烷的硅氢加成反应师彤,谢择民,王清正(中国科学院化学研究所北京100080)关键词含氢硅氧烷,二乙烯基四甲基二硅氧烷,硅氢加成反应,~1HNMR铂催化硅氢加成的机理~[1,2]、副反应 ̄[3,4]、聚合物性能 ̄[3,5]等均有报道,个别文献用粘?.. 相似文献
958.
Jacques Vervoort Dennis J. O'Kane Lionel A. Carreira John Lee 《Photochemistry and photobiology》1983,37(1):117-119
The vibrational fingerprint in the frequency region 1700-1100 cm-1 has been obtained for a fluorescent protein purified from the bioluminescent bacterium Photobacterium leiognathi. using the technique of resonance coherent anti-Stokes Raman scattering. The frequencies of the 4 prominent modes are the same as for lumazine protein purified from Photobacterium phosphoreum , and for an authentic sample of 6,7-dimethyl-8-ribityllumazine. The fluorophore in the new protein, therefore, must have the same chemical structure. The absence of frequency shifts between the free and bound ligand, in contrast to observations of fiavoproteins, implies that the lumazine ring undergoes no changes in hydrogen bonding between the free and protein-bound ligand in its ground electronic state. However, changes in relative intensities of two modes are seen, arising from differences in interactions in the excited state, and this is also reflected by differences in fluorescence properties. 相似文献
959.
An ab initio molecular orbital study, using a Gaussian basis set, of the geometries of Li2O2 and LiO2H is presented. Consistent with the experimental data available, Li2O2 is found to have a rhombic structure; the O-Li-O configuration in LiO2H is found to form an acute triangle. The bonding in these species is discussed to terms of Mulliken population analyses. 相似文献
960.
John Pisanchyn 《Journal of polymer science. Part A, Polymer chemistry》1973,11(1):135-141
An essentially alternating copolyamide of 6-aminohexanoic acid and 11-aminoundecanoic acid was obtained by the condensation polymerization of methyl 11-(6-aminohexanamido)undecanoate. The monomer was synthesized by the following reaction steps: (1) nitration of cyclohexanone to α-nitrocyclohexanone; (2) cleavage of α-nitrocyclohexanone by methyl 11-aminoundecanoate to obtain methyl 11-(6-nitrohexanamido)undecanoate; (3) hydrogenation of the nitro group of the cleavage product. The polymer was characterized by its melting and crystallization behavior as determined by differential scanning calorimetry, by x-ray analysis, and by comparison with an equimolar, random copolyamide of the two amino acids. 相似文献