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On the basis of spectral and chemical evidence it is shown that bis(cyclopentadienyl)titanium is not a sandwich-π-type compound. The most probable structure in solution is that of a dimer containing metal-metal bond and π-and σ-bonded cyclopentadienyl rings.  相似文献   
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A new synthesis of the carbapenem ring system, as found in thienamycin and related natural products, has been developed. The key step involves a highly efficient carbene insertion reaction which produces the bicyclic ring system by forming the N3 bond.  相似文献   
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Quinoxaline and 2(1H)-quinoxalones react with organomagnesium salts differently from the corresponding phthalazines and quinazolines. 3-Dimethylaminopropyl-magnesiumchloride alkylates quinoxaline easily by addition to the 2 and 3 position forming a tetrahydroquinoxaline 2 , which can be dehydrogenated to the corresponding dialkylated quinoxaline 3 . The monosubstituted dihydroquinoxaline 5 is obtained only with difficulty. It can equally be dehydrogenated, yielding 6 . Quinoxalones react with CH3MgI, C6H5MgBr, (CH3)2N? (CH2)3? MgCl by addition to the 3,4-C?N bond (not at the CO-group), yielding 11–13 . These dihydroquinoxalones are dehydrogenated to the 3-substituted 2(1H)-quinoxalones 14–16 . Only 3-phenyl-quinoxalone adds a Grignard reagent at the CO group, forming a 2-substituted 3-phenylquinoxaline ( 26 ). 3-Methyl-quinoxalone exhibits an abnormal behaviour: It is deprotonated by the mentioned reagents at the CH3 group, and the 3-methylenequinoxalone-anion so formed attacks another molecule of methylquinoxalone, finally yielding 32 and 33 .  相似文献   
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A combination of in situ surface sensitive-techniques, UV photoemission and low energy electron diffraction, with ex situ bulk sensitive X-ray diffraction reveals the formation of epitaxial thin films of sexiphenyl on Al(111) starting from the first monolayer. For room temperature growth, highly ordered films are formed with a unique alignment of the sexiphenyl molecules with the long axes of all molecules aligned parallel to both the surface and the <10> azimuthal directions of Al(111). This is related to a densely packed highly commensurate first monolayer, which acts as a template for the unique (21) crystallite orientation observed.  相似文献   
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A library of symmetrical linear oligothiophene was prepared employing decarboxylative cross‐coupling reaction as the key transformation. Thiophene potassium carboxylate salts were used as cross‐coupling partners without the need of co‐catalyst, base, or additives. This method demonstrates complete chemoselectivity and is a comprehensive greener approach compared to the existing methods. The modularity of this approach is demonstrated with the preparation of discreet oligothiophenes with up to 10 thiophene repeat units. Symmetrical oligothiophenes are prototypical organic semiconductors where their molecular electrical doping as a function of the chain length can be assessed spectroscopically. An oligothiophene critical length for integer charge transfer was observed to be 10 thiophene units, highlighting the potential use of discrete oligothiophenes as doped conduction or injection layers in organic electronics applications.  相似文献   
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A library of symmetrical linear oligothiophene was prepared employing decarboxylative cross-coupling reaction as the key transformation. Thiophene potassium carboxylate salts were used as cross-coupling partners without the need of co-catalyst, base, or additives. This method demonstrates complete chemoselectivity and is a comprehensive greener approach compared to the existing methods. The modularity of this approach is demonstrated with the preparation of discreet oligothiophenes with up to 10 thiophene repeat units. Symmetrical oligothiophenes are prototypical organic semiconductors where their molecular electrical doping as a function of the chain length can be assessed spectroscopically. An oligothiophene critical length for integer charge transfer was observed to be 10 thiophene units, highlighting the potential use of discrete oligothiophenes as doped conduction or injection layers in organic electronics applications.  相似文献   
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We use ultraviolet photoelectron spectroscopy to investigate the effect of oxygen and air exposure on the electronic structure of pentacene single crystals and thin films. It is found that O2 and water do not react noticeably with pentacene, whereas singlet oxygen/ozone readily oxidize the organic compound. Also, we obtain no evidence for considerable p-type doping of pentacene by O2 at low pressure. However, oxygen exposure lowers the hole injection barrier at the interface between Au and pentacene by 0.25 eV, presumably due to a modification of the Au surface properties.  相似文献   
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