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31.
Reaction schemes have been developed that lead to clusters having the topology of the PN cluster of nitrogenase. The single cubane clusters [(Tp)MFe3S4Cl3]z (M = Mo, z = 1-; M = V, z = 2-) react with PEt3 to give [(Tp)MFe3S4(PEt3)3]1+, which are reduced to the neutral edge-bridged double cubanes [(Tp)2M2Fe6S8(PEt3)4] with highly reduced (2[MFe3S4]1+) cores. Reaction of these clusters in acetonitrile with (Et4N)(HS) results in the formation of [(Tp)2Mo2Fe6S9(SH)2]3- and [(Tp)2V2Fe6S9(SH)2]4-. X-ray structures of the Et4N+ salts reveal the bridging pattern M2Fe6(mu2-S)2(mu3-S)6(mu6-S) in which two cuboidal MFe3(mu3-S)3 units share the common bridge atom mu6-S and are externally bridged by two mu2-S atoms. The M sites possess trigonal octahedral, and the Fe sites, distorted tetrahedral coordination. Hydrosulfide ligands and sulfide atoms simulate terminal cysteinate ligation and mu2 bridges, respectively, in the protein-bound cluster Fe8S7(mu2-SCys)2(SCys)4. The synthetic clusters have the same bridging pattern as the PN cluster and approach congruency with it. These clusters are the first molecular topological analogues of a PN cluster. Like the latter, they are substantially reduced (majority of Fe(II)). 相似文献
32.
Ma C Kwok WM Chan WS Zuo P Wai Kan JT Toy PH Phillips DL 《Journal of the American Chemical Society》2005,127(5):1463-1472
A combined femtosecond Kerr gated time-resolved fluorescence (fs-KTRF) and picosecond Kerr gated time-resolved resonance Raman (ps-KTR(3)) study is reported for two p-hydroxyphenacyl (pHP) caged phototriggers, HPDP and HPA, in neat acetonitrile and water/acetonitrile (1:1 by volume) solvents. Fs-KTRF spectroscopy was employed to characterize the spectral properties and dynamics of the singlet excited states, and the ps-KTR(3) was used to monitor the formation and subsequent reaction of triplet state. These results provide important evidence for elucidation of the initial steps for the pHP deprotection mechanism. An improved fs-KTRF setup was developed to extend its detectable spectral range down to the 270 nm UV region while still covering the visible region up to 600 nm. This combined with the advantage of KTRF in directly monitoring the temporal evolution of the overall fluorescence profile enables the first time-resolved observation of dual fluorescence for pHP phototriggers upon 267 nm excitation. The two emitting components were assigned to originate from the (1)pipi (S(3)) and (1)npi (S(1)) states, respectively. This was based on the lifetime, the spectral location, and how these varied with the type of solvent. By correlating the dynamics of the singlet decay with the triplet formation, a direct (1)npi --> (3)pipi ISC mechanism was found for these compounds with the ISC rate estimated to be approximately 5 x 10(11) s(-)(1) in both solvent systems. These photophysical processes were found to be little affected by the kind of leaving group indicating the common local pHP chromophore is largely responsible for the fluorescence and relevant deactivation processes. The triplet lifetime was found to be approximately 420 and 2130 ps for HPDP and HPA, respectively, in the mixed solvent compared to 150 and 137 ns, respectively, in neat MeCN. The solvent and leaving group dependent quenching of the triplet is believed to be associated with the pHP deprotection photochemistry and indicates that the triplet is the reactive precursor for pHP photorelease reactions for the compounds examined in this study. 相似文献
33.
RongZhongYUAN ZuoLongYU MeiZhenQU 《中国化学快报》2003,14(7):755-758
A novel gel-like process has been developed for synthesizing LiaNi0.8Co0.2O2 powders,using citric acid as a chelating agent. This process improves the homogeneity of constituent cation and enhances their reactivity in the obtained precursor. The results of electrochemical test demonstrated that these materials exhibited excellent electrochemical properties. Its initial capacity reached 181.6 mAh/g and reversible efficiency at the first cycle is about 88.6%. 相似文献
34.
JianGouHUANG ManCaiXU HaiTaoLI ZuoQingSHI 《中国化学快报》2003,14(9):914-916
Two polymeric adsorbents, poly(methyl p-vinylbenzvl ether) and oolv(ohenvl p-vinylbenzyl ether), were synthesized from chloromethylated polystyrene, Their adsorptionproperty for phenol in hexane solution was investigated. The results showed that the twoadsorbents adsorb phenol from hexane solution through hydrogen-bonding and π-π stacking interaction. 相似文献
35.
Studies on Phase Behavior of Alkyl Polyglucoside Based on Microemulsions with Modified Fishlike Phase Diagram 总被引:1,自引:0,他引:1
JinLingCHAI GanZuoLI ZhaoYuDIAO GaoYongZHANG 《中国化学快报》2004,15(3):361-364
The three-phase behavior in the quaternary system of an alkyl (C8/10^- or C12/14^-)polyglucoside / 1-butanol / n-octane / water has been studied at 40℃ with the modified fishlike phase diagram, which is presented by us for the first time. The mass fraction of 1-butanol in the hydrophile-lipophile balanced interfacial layer, A^S, the coordinates of the start point B and the end point E of the phase diagram, and the solubilities of alkyl polyglucoside and 1-butanol in n-octane phase were calculated. The solubilization of the microemulsion was also discussed. 相似文献
36.
Huang S Xiao Z Wang F Zhou J Yuan G Zhang S Chen Z Thiel W von Ragué Schleyer P Zhang X Hu X Chen B Gan L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(18):5449-5456
[60]Fullerene mixed peroxides C60(O)(OOtBu)4 exhibit chemo- and regioselective reactions under mild conditions. The epoxy moiety is opened by ferric chloride to form vicinal hydroxy chloride C60Cl(OH)(OOtBu)4. BF3 is also effective in opening the epoxy moiety. The O-O bond of the fullerene mixed peroxide is cleaved by aluminum chloride to form both [5,6]- and [6,6]-fullerene hemiketals (oxohomo[60]fullerenes). A Hock-type rearrangement is proposed for the formation of the hemiketals, in which a fullerene C-C bond is cleaved. Lewis acids and/or visible light can initiate isomerization of the hemiketal isomers. Single-crystal X-ray analysis and theoretical calculations confirmed the results. 相似文献
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