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21.
By density functional methods we characterize the bonding and charge distribution in complexes of benzene with dearomatizing agents tpReCO(L), tpMoNO(L), and tpWNO(L), where tp = hydrido Tris (pyrazolyl)borate), for a range of ligands L. Our LSDA and B3LYP density functional calculations use the Spartan LACVP+ basis and pseudopotential on Re, Mo, and W and 6-31G* on light atoms. The binding energy is strongly dependent on the nature of the ligand L, being greatest for L = ammonia and N-methylimidazole and weakest for CH3NC and CO. We find a correlation between strength of binding and electron transfer from the dearomatizing agents toward benzene. For the most strongly bound systems we find substantial (up to 500 millielectrons) charge transfer towards benzene, while for the most weakly bound systems charge is withdrawn from benzene. Structural details illustrate the ability of Re, Mo, and W species to dearomatize complexed benzene, which is extensive for all but the most weakly bound species with L = MeNC and CO. Re and W dearomatizing agents, which are computed and observed to form stable complexes with benzene, may be economic alternatives to osmium dearomatizing agents. 相似文献
22.
A novel bridged β-CD dimer in which two β-cyclodextrins were linked by a naphthalene at positions 2 and 7 has been synthesized. 1H and 13CNMR measurements showed that a large change in the conformation of the dimer occurred in aqueous solution. The dimer interacted with methyl and ethyl orange to form stable inclusion complexes via "induced fit" mechanism. 相似文献
23.
Dinuclear Silylene Bridged Cyclopentadienylrhodiumbis(ethene) Complexes, Photochemical Reaction with Benzene Derivatives, and Selective Inclusion of Methylcyclopentane into the Crystal Lattice of [Me2Si{3-But-C5H3Rh(C2H4)2}2] By reaction of [{(C2H4)2RhCl}2] with Na2[Me2Si(C5H4)2] or with Li2[Me2Si(3-But-C5H3)2] in THF the dinuclear silylene bridged complexes [Me2Si{C5H4Rh(C2H4)2}2] 1 and [Me2Si{3-But-C5H3Rh(C2H4)2}2] 2 , respectively, were synthesized. Due to the asymmetric substitution of the five-membered rings and their hindered rotation around the Si? C axes, 2 is formed as three isomers. The X-ray structure analysis of 2 obtained from hexane reveals the selective inclusion of methylcyclopentane, the content of which in the solvent is about 17%, into the crystal lattice. UV irradiation of 1 in hexane in the presence of benzene causes elimination of the ethene ligands yielding the μ-η3:η3 benzene complex [Me2Si(C5H4Rh2)2C6H6] which cannot be separated from unreacted 1 . However, separation is possible in case of the hexamethylbenzene compound 4 analogous with 3 . 相似文献
24.
Li-Juan Jia Yuan-Yuan Wang Hui Chen Yong-Kui Shan Li-Yi Dai 《Reaction Kinetics and Catalysis Letters》2005,86(2):267-273
Summary The alkylation of benzene with 1-hexene has been investigated in different triethylamine hydrochloride-ferric chloride (Et3NHCl-FeCl3) and triethylamine hydrochloride-aluminium chloride (Et3NHCl-AlCl3) ionic liquids. Both high catalyst activity and monoalkylation selectivity were observed for these two type of ionic liquids.
Systems prepared by modification with HCl in Et3NHCl-FeCl3ionic liquids prove to be very suitable solvents and catalysts for the reaction. When employing Et3NHCl-AlCl3ionic liquids as catalysts, the reaction takes place in biphasic mode with facile catalyst separation and catalyst recycling. 相似文献
25.
Fluorogenic probes dual-labeled with reporter and quencher dyes use a change in fluorescence to monitor biochemical events (e.g., substrate binding or enzyme digestion). Such events change the reporter-quencher distance, which affects fluorescence. Recently, it is has been shown that static quenching through intramolecular dimers is an important mechanism that can sometimes be more efficient than F?rster resonance energy transfer (FRET). 相似文献
26.
M. SAADIOUI Z. ASFARI J. VICENS N. REYNIER J. F. DOZOL 《Journal of inclusion phenomena and macrocyclic chemistry》1997,28(3):223-244
This article describes the synthesis, structure andUV properties of azocalixcrowns in which the photoresponsivetrans-cis azo benzene unit has been introduced in the glycolicchains of the calix[4]crowns. The synthesis proceeded via the selective-1,3O-dialkylation of calix[4]arene with glycolic chains terminated bynitrophenyl residues. After reduction of thenitro groups into amino functions,intramolecular oxidative coupling produced thecapping of the calixarene. Thesynthetic approaches and the cis-transstructure of these new ligandsare discussed and full details on synthesesand structural data are given. Apreliminary example of cesium complexation byone of the ligands is proposed. 相似文献
27.
Heat capacities (Cp) of solid benzene, biphenyl,p-terphenyl,p-quaterphenyl, and poly-p-phenylene were analyzed using the ATHAS Scheme of computation. The calculated heat capacities based on approximate vibrational spectra of solid benzene and the series of oligomers containing additional phenylene groups were compared to experimental data newly measured and from the literature to identify possible additional large-amplitude motion. The skeletal heat capacity was fitted to the Tarasov equation to obtain the one- and three-dimensional vibration frequencies 1 and 3 using a new optimization approach. Their relationship to the number of phenylene groupsn is: 1=426.0–150.3/n; and 3=55.4+81.8/n. Except for benzene, the quantitative thermal analyses do not show significant contributions from large-amplitude motion below the melting temperatures.This work was financially supported by the Div. of Materials Res., NSF, Polymers Program, Grant # DMR 90-00520 and Oak Ridge National Laboratory, managed by Lockheed Martin Energy Research Corp. for the U. S. Department of Energy, under contract number DE-AC05-96OR22464. 相似文献
28.
9 氯甲基蒽 ( 1 )与 3 ,5 二甲氧基苄醇 ( 2 )在相转移催化剂存在下反应生成 9 ( 3 ,5 二甲氧基苄基氧甲基 )蒽 ( 3 ) .( 3 )的苯溶液在紫外光照射下发生蒽环与苯环间的分子内 [4π + 4π]光致环加成反应 ,定量地生成多环化合物 ( 4 ) .( 4 )在热的作用下发生逆反应 ,定量地转化成原料 ( 3 ) .这种光致可逆反应可应用于制备光开关材料 . 相似文献
29.
30.
Alkyl ketene dimer (AKD) sizing of paper involves the redistribution of the wax over the fibre surface upon heating. The two
major mechanisms widely studied so far are the spreading of an autophobic precursor of molten AKD and AKD vapour transport
and re-deposition on the fibre surface. All previous work assumed that the transport of AKD vapour could be expressed by the
change of water contact angle with substrates that were exposed to the vapour. Information regarding the chemical composition
of the vapour phase above the AKD wax has not been found in the literature. In this work, a simple method for analysing the
chemical composition of the vapour is established. Our preliminary results indicated that the chemical composition of AKD
vapour in the temperature range of 75–80 °C is dominantly fatty acids. This suggests that the sizing effect by actual AKD
molecules via the vapour deposition mechanism is likely to be insignificant in this temperature range. This also implies that
fatty acids play a positive role in AKD sizing. The chemical stability of AKD in this temperature range is also studied. 相似文献