A novel asymmetric dinuclear gold(I) complex with 3,6-diethynylphenanthroline, 3,6-bis{(PPh3)–Au–C≡C}2-phen, has been synthesized from Au(PPh3)Cl (PPh3 = triphenylphosphine) and 3,6-diethynyl-1,10-phenanthroline. The asymmetrical dinuclear gold(I) complex, 3,6-bis{(PPh3)–Au–C≡C}2-phen, demonstrated a weak phosphorescence assignable to the metal-perturbed 3π–π* transition in the long wavelength region compared to an intense emission of the symmetrical dinuclear complex with 3,8-diethynylphenanthroline,
3,8-bis{(PPh3)–Au–C≡C}2-phen. A similar tendency of phosphorescent bands for the mononuclear gold(I) complexes with 5-ethynylphenanthroline, 5-{(PPh3)–Au–C≡C}-phen, and 3-ethynylphenanthroline, 3-{(PPh3)–Au–C≡C}-phen was observed. The absorption bands assignable to the π–π*(C≡Cphen) transition and phosphorescent emission assignable to the metal-perturbed 3π–π* transition for these four gold(I) complexes were reasonably consistent with the results calculated by DFT and TD-DFT. 相似文献
Carboxylic acids were heated at 150 °C in DMF in the presence of 1.25 equiv of thionyl chloride to give corresponding N,N-dimethylamides in good yields. Tandem chlorination and amidation reactions occurred in the one-pot procedure. Dicarboxylic acids needed prolonged reaction time to produce bisamides in good yields. Some benzamides were efficiently converted into corresponding 1,2-diaryl-1,2-diketones (benzils) under acyloin condensation conditions in the presence of 4,4′-di-tert-butylbiphenyl (DBB) in THF. Ultrasonic irradiation effectively accelerates the reaction, but it is not critical. However, the presence of DBB is fatal to the reaction. Although a few synthetic methods for benzils from benzoic acids have been reported so far, this method is one of the most convenient and highly reproducible procedures. 相似文献
The combination of vanadium-oxo compounds (3 or 4) with a lipase produced the regio- and enantioconvergent transformation of racemic allyl alcohols (1 or 2) into optically active allyl esters. In this system, the vanadium compounds catalyzed the continuous racemization of the alcohols along with the transposition of the hydroxyl group, while the lipase effected the chemo- and enantioselective esterification to achieve the dynamic kinetic resolution. 相似文献
A new class of 1,3-diphoshacyclobutane-2,4-diyls bearing alkylsulfanyl or arylsulfanyl groups together with the sterically demanding Mes* groups have been prepared as air-stable compounds.
We review some techniques and notions for quantum information theory. It is shown that the dynamical entropies is discussed
and some numerical computations of these entropies are carried for several states. 相似文献
Helical [5]thiaheterohelicene 5HM, which rapidly interconverts between P and M enantiomers in solution, was connected to helical l-phenylalanine oligomers with an ester linkage to give peptidehelicenes (5Fn, where n: number of bonded phenylalanines). The characteristics of 5F4 and 5F5 with two types of helixes in a molecule were investigated, particularly in comparison with those of 5F1–5F3 with an incomplete coil of a peptide moiety. l-Phenylalanine peptide chains induced a shift in the equilibrium between the P and M helixes of 5HM toward the P side for all the 5Fns examined. The enantiomeric excess (ee) of the P form increased with a decrease in temperature, together with an elongation of the peptide chains. 5F4 and 5F5 in hot solutions of some solvents formed a gel at room temperature, whereas 5F1–5F3 showed no such behavior. In this gel, the stable helical form of the 5HM moiety in 5F4 and 5F5 was observed to be the M form in contrast to that in their solutions. 相似文献