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231.
Anne Vessieres Daniel Touchard Pierre Dixneuf 《Journal of organometallic chemistry》1976,118(1):93-100
Heterodienetricarbonyliron complexes react with ligands ( L = PMe2Ph, P(OMe)3 or P(OPh)3) to give the adducts (enone)Fe(CO)3L with the ethylenic double bond coordinated only to the iron(0). Electron-releasing and low-steric effects of L make the reaction which is specific for enones easier compared to that for dienes. PMe2Ph allows enone exchange and P(OPh)3 promotes carbonyl elimination. Ligand influence is shown by infrared spectroscopy and by the shielding of ethylenic protons in NMR spectroscopy. 相似文献
232.
Nicola Armaroli Gianluca Accorsi JohnN. Clifford Jean‐Franois Eckert Jean‐Franois Nierengarten 《化学:亚洲杂志》2006,1(4):564-574
Oligophenylenevinylene (OPV)‐terminated phenylenevinylene dendrons G1 – G4 with one, two, four, and eight “side‐arms”, respectively, were prepared and attached to C60 by a 1,3‐dipolar cycloaddition of azomethine ylides generated in situ from dendritic aldehydes and N‐methylglycine. The relative electronic absorption of the OPV moiety increases progressively along the fullerodendrimer family C60G1 – C60G4 , reaching a 99:1 ratio for C60G4 (antenna effect). UV/Vis and near‐IR luminescence and transient absorption spectroscopy was used to elucidate photoinduced energy and electron transfer in C60G1 – C60G4 as a function of OPV moiety size and solvent polarity (toluene, dichloromethane, benzonitrile), taking into account the fact that the free‐energy change for electron transfer is the same along the series owing to the invariability of the donor–acceptor couple. Regardless of solvent, all the fullerodendrimers exhibit ultrafast OPV→C60 singlet energy transfer. In CH2Cl2, the OPV→C60 electron transfer from the lowest fullerene singlet level (1C60*) is slightly exergonic (ΔGCS≈0.07 eV), but is observed, to an increasing extent, only in the largest systems C60G2 – C60G4 with lower activation barriers for electron transfer. This effect has been related to a decrease of the reorganization energy upon enlargement of the molecular architecture. Structural factors are also at the origin of an unprecedented OPV→C60 electron transfer observed for C60G3 and C60G4 in apolar toluene, whereas in benzonitrile, electron transfer occurs in all cases. Monitoring of the lowest fullerene triplet state by sensitized singlet oxygen luminescence and transient absorption spectroscopy shows that this level is populated through intersystem crossing and is not involved in photoinduced electron transfer. 相似文献
233.
Lei He Hui‐Min Liu Xiao‐Lan Luo Wen‐Qin Zhang 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(2):o104-o106
The title compound, 2‐{N‐[2‐(2‐hydroxybenzamido)ethylammonioethyl]aminocarbonyl}phenolate, C18H21N3O4, crystallizes in a zwitterionic form as a result of intermolecular proton transfer and possesses a negatively charged phenolate group and a protonated amino group. The 2‐hydroxybenzamide and 2‐(aminocarbonyl)phenolate moieties attached to the two ends of the C—C—N—C—C backbone adopt a cis conformation in relation to this backbone. All N‐ and O‐bound H atoms are involved in hydrogen‐bond formation; the zwitterions are first linked into head‐to‐tail dimers, which are further organized into a two‐dimensional network parallel to the crystallographic bc plane. 相似文献
234.
Product distributions and rate constants for the reaction of ground state C+ ions with O2, NO, HCl, CO2, H2S, H2O, HCN, NH3, CH4, H2CO, CH3OH, and CH3NH2 have been measured. Rate constants were obtained using ion cyclotron resonance trapped ion methods at JPL, and product distributions were obtained using a tandem (Dempster-ICR) mass spectrometer at the University of Utah. Rapid carbon isotope exchange has also been observed in C+-CO collisions. 相似文献
235.
The symmetric and unsymmetric phenylchlorohydrodigermanes can be isolated or characterized via partial halogenation of the Ge? H bonds of the symmetrical phenylhydrodigermanes Ph2(H)GeGe(H)2Ph, Ph(H)2GeGe(H)2Ph by chloromethyl methyl ether and carbontetrachloride. Some of these phenylchlorohydrodigermanes are formed by insertion of phenylchlorogermylene (PhGeCl) on the Ge? H or Ge? Cl bonds of the phenylchlorohydrogermanes. The hydrolysis of the monochloro phenylhydrodigermanes Ph2(Cl)GeGe(H)2 and Ph(Cl)(H)GeGe(H)2Ph leads to the phenyl phenylhydrogermyl digermoxanes [Ph2(H)GeGePh2]2O and [Ph(H)2GeGe(H)Ph]2O. Treatment of these oxides with the concentrated aqueous solutions of hydracides leads to the monofluorinated, brominated and iodinated phenylhydrodigermanes Ph2(H)GeGe(X)Ph2 and Ph(H)2GeGe(H)(X)Ph (X) = F, Br, I). Phenylchlorohydrodigermanes decompose thermally by α-elimination on one germanium atom with formation of germylene and phenylchlorohydrogermane. The physico-chemical IR. and NMR. study of these phenylhalogenohydrodigermanes indicates that, if the vGe? H frequency variations are mostly linked to the inductive effects of the substituents on the same germanium, the variations of the chemical shifts of the Ge? H protons seem to be due to many factors and especially to the inductive effect of the substituents on the germanium and the magnetic anisotropy of the Ge? X bonds. 相似文献
236.
P. Netchitailo Bernard Decroix Jean Morel Paul Pastour 《Journal of heterocyclic chemistry》1978,15(2):337-342
We describe the first synthesis of 2-arylbenzo[4,5]thieno-[2,3-b]pyran-4-one and of 2-arylbenzo [4,5] thieno [3,2-b] pyran-4-one, from benzo [4,5] thiophene and we have extended these cyclizations to obtain the heterocyclic analogs of the xanthones. 相似文献
237.
Pierre A. Vuillermot 《Communications in Mathematical Physics》1980,76(1):1-26
For any initial spin configuration we prove the existence, unicity and regularity properties of the solution of Hamilton's equations for the infinite classical Heisenberg model with stable interactions, along with the essential selfadjointness of the associated Liouville operator. We also prove new properties of SU (2)-coherent states which, together with the concept of Trotter approximations for one-parameter (semi-) groups, are used to show that this dynamics is nothing but the classical limit of the time evolution generated by the infinite quantum (suitably normalized) Heisenberg Hamiltonian. The classical limit emerges when the spin magnitude S goes to infinity while Plank's constant goes to zero, their product S remaining fixed. The main results are stated in the form of intertwining relations between the classical and the quantum unitary group.Work supported in part by the Swiss National Science Foundation under Grant 820-436-76 and in part by the U.S. Department of Energy under contract EG-77-C-03-1538. 相似文献
238.
Non-aqueous capillary electrophoresis of the positional isomers of a sulfated monosaccharide 总被引:2,自引:0,他引:2
Descroix S Varenne A Goasdoue N Abian J Carrascal M Daniel R Gareil P 《Journal of chromatography. A》2003,987(1-2):467-476
A non-aqueous capillary electrophoresis (NACE) method coupled to indirect absorbance detection has been developed for the separation of the three positional isomers of monosulfated fucose. The optimized electrolyte was composed of 12 mM ethanolamine, 2 mM trimesic acid buffer in a methanol-ethanol (1:1, v/v) mixture. As the retained electrolyte entails no separating agent other than the pH buffer, the NACE separation of the positional isomers has been ascribed mainly to selective ion-pairing with the electrolyte counter-ion and the possibility of a selective solvation effect in the alcohol mixture. In the absence of pure isomeric standards, peak identification was completed by MS and NMR spectroscopy and selective enzymatic desulfation. This method should be of interest for the structure elucidation of monosulfated fucose-based polysaccharides and for the screening of sulfoesterase of unknown activity. 相似文献
239.
Reactions of the substituted 2‐formyl chromones with aroylhydrazines gave corresponding 2‐(aroylhydrazonomethylidyne) chromones. Then 2‐(3′‐acetyl‐5′‐aryl‐2′,3′‐dihydro‐1′,3′,4′‐oxadiazol‐2′‐yl) chromones were prepared by these 2‐(aroylhydrazonomethylidyne) chromones under refluxing with Ac2O. All target compounds were characterized through elemental analysis and IR, 1H NMR, MS. 相似文献
240.
The preparation of 5,6-bis((E)-chlorommethylidene)bicyclo[2.2.2]oct-2-ene ( 13 ), 2,3-bis((E)-chloromethyl idene)-5exo,6exo- and -5endo,6endo-epoxybicyclo[2.2.2] octane ( 14 and 15 ), 5,6-bis((E)-chloromethylidene)-2exo- and -2endo-bicyclo[2.2.2] octanol ( 16 and 17 ) and 5,6-bis((E)-chloromethylidene)-2-bicyclo[2.2.2]octanone ( 18 ) are described. The face selectivity (endo-face vs. exo-face attack onto the exo-cyclic diene) of their cycloadditions to tetracyanoethylene has been determined in benzene at 20°. It is 78/22, 80/20, 60/40, 68/32, 3/97 and 30/70 for 13 , 14 , 15 , 16 , 17 and 18 , respectively. 相似文献