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51.
Diekers M Luo C Guldi DM Hirsch A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(4):979-991
For the first time several T(h)-symmetrical hexakisadducts of C(60) bearing up to six electro- and photoactive o-phenylene diamine or 9,10-dialkoxyanthracene moieties were synthesized and subjected to photoinduced electron/energy-transfer studies. Both donors form a densely packed pi-donor shell surrounding the fullerene core. In these novel core-shell ensembles (7 and 19), either an efficient energy transfer from the dialkoxyanthracene periphery, or an electron transfer from the o-phenylene diamine periphery transduces the flow of excited-state energy or electrons, respectively, to the fullerene moiety, which resides in the central core. Due to the relatively high reduction potential of the fullerene core, which is anodically shifted by approximately equal to 0.7 V, compared with that of pristine C(60), the outcome of these intramolecular reactions depends mainly on the donor ability of the peripheral system. Interestingly, the charge-separated state in the o-phenylene diamine heptad (7; tau=2380 ns in benzonitrile) is stabilized by a factor of 20 relative to the corresponding o-phenylene diamine dyad (6; tau=120 ns in benzonitrile), an effect that points unequivocally to the optimized storage of charges in this highly functionalized fullerene ensemble. 相似文献
52.
Using ring closing metathesis (RCM) as the key operation, a rapid access to β-lactams fused to a sultam moiety of variable ring size was developed from low cost, commercially available starting materials. An efficient RCM of 4-vinyl-azetidin-2-ones to give 1-aza-bicyclo[4.2.0]oct-4-en-8-ones is also reported. 相似文献
53.
Sandra Hübner Dirk Michalik Dr. Haijun Jiao Dr. Helfried Neumann Dr. Stefan Klaus Dirk Strübing Dr. Anke Spannenberg Dr. Matthias Beller Prof. Dr. 《化学:亚洲杂志》2007,2(6):734-746
Chiral N‐dienyl lactams are crucial building blocks for the synthesis of complex organic compounds. However, their generation is rather challenging. This paper reports the novel one‐pot reaction of (S)‐methyl pyroglutamate as the a mide component with different a ldehydes and d ienophiles (AAD reaction) to give novel chiral 1‐amido‐2‐cyclohexenes. The corresponding N‐dienyl lactams generated in situ undergo subsequent Diels–Alder reactions in good yield and diastereoselectivity. The scope and limitations of the three‐component protocol were investigated. X‐ray and NMR spectroscopic analysis of the products as well as DFT calculations of the intermediates were also performed to explain the observed stereoselectivity and structural features. 相似文献
54.
Substituted 2-aminoindenes have been synthesized in almost quantitative yields by reactions of amines such as methylpiperazine, trimethylethylenediamine, 1,4-diaza-cycloheptane and N,N′-dimethylethylenediamine with 2-indanone. The 2-aminoindenes can be deprotonated and reacted with BrMn(CO)3(Py)2 to produce the respective aminoindenyl-cymantrenes in yields between 55–70%. The X-ray crystal structures of 2-(methylpiperazine)indenyl-cymantrene 5 (P1 , a = 12.667(3) Å, b = 16.630(3) Å, c = 17.382(3) Å, α = 72.70(3)°, β = 74.59(3)°, γ = 88.66(3)°, V = 3364.1(12) Å 3, Z = 8, R1(2σ(I)) = 4.02%, wR2(2σ(I)) = 10.30%) and the HClO4 adduct of 2-(trimethylethylenediamine)-indenyl-cymantrene 6 (Cc, a = 23.722(5) Å, b = 6.9080 Å, c = 13.264 Å, β = 111.77(3)°, V = 2018.6(7) Å 3, Z = 4, R1(2σ(I)) = 2.94%, wR2(2σ(I)) = 7.90%) were determined. In both complexes the indenyl-carbon bonded to nitrogen displays significantly longer bonds to manganese [223.5(3)–225.8(3) pm] than the other four carbon atoms [213.3(3)–219.1(3) pm]. The short indenyl-nitrogen bonds of 136.2(4) and 137.8(4) pm are indicative of a substantial multiple bond character. The complexation of Zn2+ by the nitrogen atoms of 6 results in significant shifts of the CO stretching frequencies. 相似文献
55.
Bouchoux G Defaye D McMahon T Likholyot A Mó O Yáñez M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(13):2900-2909
The various protonated forms of phenol (1), catechol (2), resorcinol (3), and hydroquinone (4) were explored by ab initio quantum chemical calculations at the MP2/6-31G(d) and B3LYP/6-31G(d) levels. Proton affinities (PA) of 1-4 were calculated by the combined G2(MP2,SVP) method, and their gas-phase basicities were estimated after calculation of the change in entropy on protonation. These theoretical data were compared with the corresponding experimental values determined in a high-pressure mass spectrometer. This comparison confirmed that phenols are essentially carbon bases and that protonation generally occurs in a position para to the hydroxyl group. Resorcinol is the most effective base (PA = 856 kJ mol-1) due to the participation of both oxygen atoms in the stabilization of the protonated form. Since protonation is accompanied by a freezing of the two internal rotations, a significant decrease in entropy is observed. The basicity of catechol (PA = 823 kJ mol-1) is due to the existence of an intramolecular hydrogen bond, which is strengthened upon protonation. The lower basicity of hydroquinone (PA = 808 kJ mol-1) is a consequence of the fact that protonation necessarily occurs in a position ortho to the hydroxyl group. When the previously published data are reconsidered and a corrected protonation entropy is used, a proton affinity value of 820 kJ mol-1 is obtained for phenol. 相似文献
56.
Metal-chelating properties-in the ground and excited states-of fullerenocalix[4]arenes containing two malonamide substituents at the upper rim and four alkyl ester chains at the lower rim have been studied by means of steady-state absorption, fluorescence spectroscopy, and time-resolved transient absorption spectra. In particular, the influence that Ag+ enforces on the fullerene electronic spectra is due to direct interactions between Ag+ and the surface of C60. The effects stemming from Na+, Mg2+, and Ba2+, on the other hand, are indirect and are introduced through chelating the metal ions to the calix[4]arene moiety. They strongly depend on the molecular structure of the fullerenocalix[4]arenes. No spectroscopic evidence was obtained for any influence caused by Mn2+, although the malonamide groups provide good chelating ability even for this transition metal ion. 相似文献
57.
Dirk Reinen 《Monatshefte für Chemie / Chemical Monthly》1965,96(2):730-739
Zusammenfassung Für das oktaedrisch koordinierte Co2+-Ion werden ein Termschema und Energiegleichungen für zwei charakteristischeDq/B-Werte angegeben und mit deren Hilfe aus den Spektren der Co2+-haltigen Ilmenite MgTiO3 und CdTiO3
1 die Zuordnung des intensitätsstärksten Quartett-Dublett-Überganges (
a
4
T1g
b
2
T1g) auf eindeutige Weise ermöglicht.Weiter wird das spektrale Verhalten der Mg1–x
CO
x
O-Mischkristalle (0,05x1,0) in Abhängigkeit von der Co2+-Konzentration untersucht. Die Änderungen der Bandenintensitäten und desRacah-ParametersB werden wie in der analogen MgO-NiO-Mischkristallreihe2 auf Spin-Spin-Wechselwirkungen der über Sauerstoff benachbarten Co2+-Ionen zurückgeführt.
Mit 3 Abbildungen 相似文献
The energy levels of the octahedrally coordinated Co2+-ion and energy equations for two characteristicB-values are given, which allow to identify the quartet-doublet-transition ( a 4 T1g b 2 T1g) of the highest intensity from the spectrum of the Co2+ containing ilmenites MgTiO3 and CdTiO3 1.In addition, the variation of the spectra of the Mg1–x Co x O-mixed crystals (0.05x1.0) with the Co2+ concentration is investigated. The changes in the intensities of the absorption bands and of theRacah-parameterB are (as for the corresponding MgO-NiO-mixed crystals2 interpreted as being caused by spin-spin-interactions between Co2+ ions bonded to the same oxygen.
Mit 3 Abbildungen 相似文献
58.
Van den Eynde I Van Rompaey K Lazzaro F Tourwé D 《Journal of combinatorial chemistry》2004,6(4):468-473
Starting from Boc-o-aminomethylphenylalanine, a solution-phase parallel synthesis of 2,4-substituted 4-amino-1,2,4,5-tetrahydro-2-benzazepine-3-ones is described. This heterocycle has two nitrogen functions, which are differentiated and can be selectively substituted. The sources of diversity are aldehydes for the R(1) position and carboxylic acids, sulfonyl chlorides, or isocyanates for the R(2) position. High-throughput synthesis and purification of this multistep synthetic sequence was accomplished using polymer-bound reagents and scavengers and liquid-liquid extraction protocols, and a small library of compounds was prepared. Polymer-bound cyanoborohydride was found to work well for the reductive amination. Scavenging of excess of amine was performed by polymer-bound benzaldehyde, and cyclization was performed in the presence of polymer-bound coupling reagent 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC). After Boc-deprotection, the second nitrogen can be acylated using carboxylic acids, sulfonylated or converted to a urea. The acylation is again performed by polymer-bound EDC. Excellent yields and purities were obtained. 相似文献
59.
Austen K FlattShawn M Dirk Jay C HendersonDwanleen E Shen Jie SuMark A Reed James M Tour 《Tetrahedron》2003,59(43):8555-8570
Several new classes of oligomers have been synthesized with functionalities designed to aid in the understanding of molecular device behavior, specifically when molecules are interfaced between proximal electronic probes. The compounds synthesized are series of azobenzenes, bipyridines and oligo(phenylene vinylene)s that bear acetyl-protected thiols for ultimate attachment to metallic surfaces. Some initial electrochemical and solid-state test results are also reported. 相似文献
60.
Two-dimensional (2-D) Blue Native/SDS gel electrophoresis combines a first-dimensional separation of monomeric and multimeric proteins in their native state with a second denaturing dimension. These high-resolution 2-D gels aim at identifying multiprotein complexes with respect to their subunit composition. We applied this method for the first time to analyze two human platelet subproteomes: the cytosolic and the microsomal membrane protein fraction. Solubilization of platelet membrane proteins was achieved with the nondenaturing detergent n-dodecyl-beta-D-maltoside. To validate native solubilization conditions, we demonstrated the correct assembly of the Na,K-ATPase, a functional multimeric transmembrane protein, when expressed in Xenopus oocytes. We identified 63 platelet proteins after in-gel tryptic digestion of 58 selected protein spots and liquid chromatography-coupled tandem mass spectrometry. Nine proteins were detected for the first time in platelets by a proteomic approach. We also show that this technology efficiently resolves several known membrane and cytosolic multiprotein complexes. Blue Native/SDS gel electrophoresis is thus a valuable procedure to analyze specific platelet subproteomes, like the membrane(-bound) protein fraction, by mass spectrometry and immunoblotting and could be relevant for the study of protein-protein interactions generated following platelet activation. 相似文献