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81.
Z. Guennoun A. Coupeaud I. Couturier-Tamburelli N. Pitri S. Coussan J.-P. Aycard 《Chemical physics》2004,300(1-3):143-151
The structures and energies of the 1:1 acetylene/cyanoacetylene, acetylene/dicyanoacetylene and cyanoacetylene/dicyanoacetylene complexes in solid argon matrices have been investigated using FT-IR spectroscopy and ab initio calculations, at the B3LYP/6-31G** level of theory. For the three complexes, predicted frequency shifts for the L shaped structures, characterized by a hydrogen bond between the nitrogen of the cyano group and the acetylenic proton, were found to be in good agreement with those experimental. Only in the case of acetylene/cyanoacetylene complex, we obtained a second minimum with a T shaped structure characterized by an interaction between the proton of cyanoacetylene and the Π system of acetylene. It appears clearly that HC3N acts as an electrophile or as a nucleophile in these complexes. 相似文献
82.
The Cr-Cr singly-bonded dimers [{η5-RC5H4Cr(CO)3}2] (1, R=Me; 2, R=CO2Et) reacted with an equivalent of elemental selenium in THF at room temperature to give the linear Cr2Se complexes [{η5-RC5H4Cr(CO)2}2Se] (3, R=Me; 4, R=CO2Et), whereas the linear Cr2Se complex (5, R=MeCO) reacted with excess NaBH4, Ph3PCHPh or 2,4-dinitrophenylhydrazine under respective conditions to afford the linear Cr2Se derivatives [{η5-RC5H4Cr(CO)2}2Se] (6, R=MeCH(OH); 7, R=PhCHCMe; 8, R=2,4-(NO2)2C6H3NHNCMe). Similarly, while the butterfly Cr2Se2 complexes [{η5-RC5H4Cr(CO)2}2Se2] (9, R=Me; 10, R=CO2Et) could be produced either by reaction of dimers 1 and 2 with an excess amount of elemental selenium, or by reaction of the linear complexes 3 and 4 with an equivalent of elemental selenium, the butterfly Cr2Se2 derivatives [{η5-RC5H4Cr(CO)2}2Se2] (12, R=MeCH(OH); 13, R=PhCHCMe; 14, R=2,4-(NO2)2C6H3NHNCMe) were yielded by reaction of the butterfly Cr2Se2 complex (11, R=MeCO) with an excess quantity of NaBH4, Ph3PCHPh and 2,4-dinitrophenylhyazine. Both the linear complexes 3, 4, 6-8 and the butterfly complexes 9, 10, 12-14 are new, which have been fully characterized by elemental analysis, spectroscopy and X-ray crystallography. 相似文献
83.
The ENDOR spectrum of ~(14)N-~(63)Cu-HAP complex in DMSO/EtOH (5:1) freezing solution at 20 K has been studied using orientational selective method in this paper. The anisotropic superhyperfine coupling tensor and qusdrupole coupling tensor of ligand ~(14)N nucleus, and the superhyperfine coupling tensor of various ~1H nuclei have been measured precisely. Comparing the superhyperfine coupling tensor of ~(14)N-nucleus with previous work shows that the analytical method of spectrum is reasonable and the data are reliable in our previous work. 相似文献
84.
Zi-Zhong Li Qing-Xiang Guo Tan Ren Xiao-Qing Zhu You-Cheng Liu 《Journal of inclusion phenomena and macrocyclic chemistry》1993,15(1):37-42
Tetramethylsilane (TMS) can be included by -cyclodextrin (-CD), and sodium 2,2-dimethylsilapentane-5-sulphonate (DSS) can form inclusion complexes with - and -CD. The NMR chemical shifts are changed considerably as a result of the strong interaction between CD and the guest compound in the inclusion complexes. A downfield shift of as much as 0.63 ppm shift downfield has been observed for the protons of external TMS in CD aqueous solution. In view of this, the question arises of whether TMS and DSS can be used as internal references. DSS in D2O is suggested as an external reference for aqueous cyclodextrin solution in NMR measurements. 相似文献
85.
Cao Ning-Jun Xu Qin Chen Chee-Shan Gong C. S. Chen L. F. 《Applied biochemistry and biotechnology》1994,(1):521-530
Cellulose gel with < 10% of crystallinity was prepared by treatment of microcrystalline cellulose, Avicel, with zinc chloride
solution at a ratio of zinc chloride to cellulose from 1.5 to 18 (w/w). The presence of zinc ions in the cellulose gels enhanced
the rate of hydrolysis and glucose yield. The evidence obtained from X-ray diffraction, iodine absorption experiments; and
Nuclear Magnetic Resonance spectra analysis suggested the presence of zinc-cellulose complex after Avicel was treated with
zinc chloride. Zinc-cellulose complex was more susceptible to hydrolysis than amorphous cellulose. Under the experimental
condition, cellulose gels with zinc ions were hyrolyzed to glucose with 95% theoretical yield and a concentration of 14% (w/v)
by cellulases within 20 h. The same gel was hydrolyzed by acid to glucose with 91.5% yield and a concentration of 13.4% (w/v). 相似文献
86.
Organophosphorus compounds have been applied in two ways in chemical synthesis. They can either be used as a reagent in a step of the synthesis (for example, in the Wittig reaction) or they can be incorporated directly into the target molecule. This second application, in particular, has expanded greatly in the last few years with the preparation of low-coordination phosphorus compounds. These include the phosphaalkynes, which are of great interest to organic and inorganic chemists. Phosphaalkynes have been employed in the synthesis of heterocyclic compounds, phosphaarenes and their valence isomers, and polycyclic compounds. Further applications have been the use of phosphaalkynes as new ligand systems in complex chemistry and their cyclooligomerization with organometallic reagents. While the chemical properties of phosphaalkynes have little in common with those of nitriles, they are in many ways very similar to those of the isoelectronic acetylenes. 相似文献
87.
Luo J Zheng QY Chen CF Huang ZT 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(20):5917-5928
A series of inherently chiral calix[4]arenes with cone and partial cone conformations and with crown ether moieties of variable size have been readily synthesized. By taking advantage of the carboxy appendage on the lower rim, these were condensed with the chiral auxiliary (S)-BINOL to form diastereomers which, in most cases, could be separated by preparative TLC, or more desirably, by column chromatography on silica gel (diastereomeric excess >99 % based on HPLC analysis). Seven enantiopure antipodes of inherently chiral calix[4]crowns were obtained after hydrolysis. It has been found that both the size of the crown moiety and alkylation of the last phenolic hydroxy group (accompanied with or without a change in the conformation) affect the separation of the diastereomers. 相似文献
88.
The Mitsunobu reaction is a widely used and versatile method for the dehydrative oxidation–reduction condensation of an acid/pronucleophile usually with a primary or secondary alcohol that requires the combination of a reducing phosphine reagent together with an oxidizing azo reagent. The utility of this reaction stems from the fact that it is generally highly stereoselective and occurs with inversion of the stereochemical configuration of the alcohol starting material. Furthermore, as carboxylic acids, phenols, imides, sulfonamides, and other compounds can be used as the acid/pronucleophile, this reaction is useful for the preparation of a wide variety of functional groups. This Focus Review of the Mitsunobu reaction summarizes its origins, the current understanding of its mechanism, and recent improvements and applications. 相似文献
89.
A simplified procedure based on ion-exchange separation of selenourea (Se-U) and selenocystamine (Se-CM), which have very close half-wave potential when they are simultaneously analyzed by voltammetric techniques, has been developed and optimized. Thus, selenocystamine remains in the cation exchanger Purolite C 100 H, whereas selenourea is found in the effluent and is determined by square wave cathodic stripping voltammetry using Na2CO3 as electrolyte. Selenocystamine is then eluted from the cation exchanger using 4 M HCl and analyzed by square wave cathodic stripping voltammetry in the HCl solution. For each voltammetric determination the corresponding parameters were investigated and optimized; the obtained detection limits were 0.3 ng Se mL–1 for Se-CM and 2 ng Se mL–1 for Se-U. A flow sheet for the separation of inorganic (Se(IV) and Se(VI)) and organoselenium compounds (Se-U, Se-CM, (CH3)2Se2, and (CH3)2Se) developed for their electrochemical detection is presented and it was successfully applied to a certified reference material, an environmental soil sample, and a urine sample. 相似文献
90.