3-(2-Alken-1-one-2-yl)indoles through the palladium-catalyzed reaction of 2-alkynyltrifluoroacetanilides with cyclic α-iodoenones

α-Iodoenones can be efficiently employed as organic electrophiles in the Pd-catalyzed synthesis of 2,3-disubstituted indoles from 2-alkynyltrifluoroacetanilides. Best results were obtained using the weak ligand As(Ph)₃. The methodology reported provides an efficient entry to indoles bearing a 2-alkenon-2-yl moiety linked in the 3-position, that possesses a scarcely reported substitution pattern.     

Molecular structure and benzene ring deformation of three ethynylbenzenes from gas-phase electron diffraction and quantum chemical calculations

The molecular structures of ethynylbenzene and s-triethynylbenzene have been accurately determined by gas-phase electron diffraction and ab initio/DFT MO calculations and are compared to that of p-diethynylbenzene from a previous study [Domenicano, A.; Arcadi, A.; Ramondo, F.; Campanelli, A. R.; Portalone, G.; Schultz, G.; Hargittai, I. J. Phys. Chem. 1996, 100, 14625]. Although the equilibrium structures of the three molecules have C2v, D3h, and D2h symmetry, respectively, the corresponding average structures in the gaseous phase are best described by nonplanar models of Cs, C3v, and C2v symmetry, respectively. The lowering of symmetry is due to the large-amplitude motions of the substituents out of the plane of the benzene ring. The use of nonplanar models in the electron diffraction analysis yields ring angles consistent with those from MO calculations. The molecular structure of ethynylbenzene reported from microwave spectroscopy studies is shown to be inaccurate in the ipso region of the benzene ring. The variations of the ring C-C bonds and C-C-C angles in p-diethynylbenzene and s-triethynylbenzene are well interpreted as arising from the superposition of independent effects from each substituent. In particular, experiments and calculations consistently show that the mean length of the ring C-C bonds increases by about 0.002 A per ethynyl group. MO calculations at different levels of theory indicate that though the length of the C[triple bond]C bond of the ethynyl group is unaffected by the pattern of substitution, the C(ipso)-C(ethynyl) bonds in p-diethynylbenzene are 0.001-0.002 A shorter than the corresponding bonds in ethynylbenzene and s-triethynylbenzene. This small effect is attributed to conjugation of the two substituents through the benzene ring. Comparison of experimental and MO results shows that the differences between the lengths of the C(ipso)-C(ethynyl) and C(ipso)-C(ortho) bonds in the three molecules, 0.023-0.027 A, are correctly computed at the MP2 and B3LYP levels of theory but are overestimated by a factor of 2 when calculated at the HF level.     

Mechanism of copper underpotential deposition at Pt(<Emphasis Type="Italic">hkl</Emphasis>)-electrodes: Quantum-chemical modelling

Mechanism of copper underpotential deposition at stepped faces of platinum single crystals Pt(hkl) is studied using cyclic voltammetry, scanning probe microscopy, and quantum-chemical modelling. It is shown that the first stage of UPD is one-dimensional decoration of the (100)- or (110)-orientated steps, then copper monolayer forms at (111)-terraces. The final stage is the secondary step decoration. Quantum-chemical modelling, with the using of long-distance potentials of the Cu-Pt and Cu-Cu pair interactions, allows estimating the energy of copper adsorption at different structure elements of the substrate (steps, kinks, terraces) and revealing the succession of the adatom monolayer formation; it also provides additional information for the identifying of the nature of voltametric peaks for different stages of the copper adsorption-desorption.     

求解复杂湍流的非线性涡黏性系数模型和代数应力模型

非线性涡黏性系数模型和代数应力模型联系了线性涡黏性系数湍流模型和完整的微分 雷诺应力模型.随着它们受到日益关注,其形式也越来越多样化.本篇综述的目的是对这些模 型加以总结并比较它们之间的共同点及不同之处,指出它们与完整微分雷诺应力模型之间的 关系,以及相对于线性涡黏性系数模型而言它们在预报流场上所具有的优势.     

Sequential gold-catalyzed reactions of 1-phenylprop-2-yn-1-ol with 1,3-dicarbonyl compounds

A variety of sequential gold-catalyzed reactions of 1-phenylprop-2-yn-1-ol with 1,3-dicarbonyl compounds are directed towards different outcomes by a suitable choice of the catalytic system, feature of 1,3-dicarbonyl and reaction conditions.     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

Palladium catalyzed synthesis of 4-substituted-2-phenylimidazoles from N-propargyl-benzamidine

Preliminary results of an original approach to 4-substituted-2-phenylimidazoles starting from readily available N-propargyl-benzamidine and aryl halides are reported. Best yields were obtained using aryl halides bearing an electron-withdrawing group. Plausible mechanisms are also discussed.