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31.
《Magnetic resonance in chemistry : MRC》2003,41(6):417-430
A systematic study of the one‐bond and long‐range J(C,C), J(C,H) and J(H,H) in the series of nine bicycloalkanes was performed at the SOPPA level with special emphasis on the coupling transmission mechanisms at bridgeheads. Many unknown couplings were predicted with high reliability. Further refinement of SOPPA computational scheme adjusted for better performance was carried out using bicyclo[1.1.1]pentane as a benchmark to investigate the influence of geometry, basis set and electronic correlation. The calculations performed demonstrated that classical ab initio SOPPA applied with the locally dense Dunning's sets augmented with inner core s‐functions used for coupled carbons and Sauer's sets augmented with tight s‐functions used for coupled hydrogens performs perfectly well in reproducing experimental values of different types of coupling constants (the estimated reliability is ca 1–2 Hz) in relatively large organic molecules of up to 11 carbon atoms. Additive coupling increments were derived for J(C,C), J(C,H) and J(H,H) based on the calculated values of coupling constants within SOPPA in the model bicycloalkanes, in reasonably good agreement with the known values obtained earlier on pure empirical grounds. Most of the bridgehead couplings in all but one bicycloalkane appeared to be essentially additive within ca 2–3 Hz while bicyclo[1.1.1]pentane demonstrated dramatic non‐additivity of ?14.5 Hz for J(C,C), +16.6 Hz for J(H,H) and ?5.5 Hz for J(C,H), in line with previous findings. Non‐additivity effects in the latter compound established at the SOPPA level should be attributed to the through‐space non‐bonded interactions at bridgeheads due to the essential overlapping of the bridgehead rear lobes which provides an additional and effective non‐bonding coupling path for the bridgehead carbons and their protons in the bicyclopentane framework. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
32.
Tsutomu KumagaiMasaaki Tomura Jun-ichi NishidaYoshiro Yamashita 《Tetrahedron letters》2003,44(36):6845-6848
1,3-Dithiol-2-ylidene derivatives containing bis(ethynylpyridine) units were synthesized using a Pd-catalyzed reaction of the corresponding dibromide. X-Ray crystal analysis revealed unique crystal structures depending on the aromatic groups. The absorption spectra and redox properties indicated intramolecular charge-transfer interactions between the 1,3-dithiole unit and the pyridyl parts. 相似文献
33.
李永祥 《数学物理学报(A辑)》2003,23(2):245-252
该文讨论四阶常微分方程边值问题u^(4)(t)=f(t,u,u″), t∈[0,1],u(0)=u(1)=u″(0)=u″(1)=0解的存在性, 其中f(t,u,v):[0,1]×R×R→R为Carathéodory函数. 在不限制f关于u,v的增长阶, 不假定f关于u,v的单调性的一般情形下, 用上下解方法获得了解的存在性结果,并讨论了单调迭代求解的有效性. 相似文献
34.
基于相对论平均场理论,研究了各种相互作用参数组(NL1、NL3、NLSH、TM1和GL-97)对中子星物质的性质和中子星整体结构的影响.发现参数组NL1、NL3和NLSH所给出的中子星内部的介子场强度、物质的组成比例、物态方程和中子星的整体特点基本相同,但与TM1和GL-97之间有较大的差别.相对于其他参数组,GL-97给出的介子场强度最弱,中子星的相对数密度最大,物态方程也最软,同时采用GL-97参数组计算的中子星的最大质量也最小. 相似文献
35.
锥形光纤间耦合特性的分析与检测 总被引:2,自引:0,他引:2
将通信光纤的末端拉制成锥形,利用光信号在光纤锥形区特有的传输和耦合特性,实现了光纤的耦合、连接和分束。用耦合模理论分析了锥形光纤间的传输和耦合性质,给出了光信号两锥形光纤间的耦合与两锥形光纤的距离和锥形区重叠长度等实验结果。 相似文献
36.
Jacek Doskocz Jadwiga Sołoducho Joanna Cabaj Mieczysław Łapkowski Sylwia Golba Krystyna Palewska 《Electroanalysis》2007,19(13):1394-1401
A convenient and higher yielding synthetic route to N‐alkyl‐bis(thiophene)phenothiazine derivatives is reported and their aggregation, electrochemical properties and polymerization are characterized. The key step in the synthesis of this group of compounds has been the Stille type coupling reaction between the N‐alkyldibromophenothiazine and tin derivatives of thiophene as the best way for preparation of conjugated N‐alkylphenothiazine derivatives. For this group of compounds we also present an electrochemical polymerization effect and widely adopted approach to prepare structurally ordered thin, electroconducting films by Langmuir–Blodgett technique. 相似文献
37.
Aminonaphthols are easily transformed into a variety of 1- and 2-naphthyl piperazines using a sequence of diazotization, iodide substitution and Pd(0) catalyzed coupling reactions. 相似文献
38.
Sébastien Lemaire Giuliano Giambastiani Barbara Pacini Giovanni Poli 《Journal of organometallic chemistry》2003,687(2):291-300
A new type I palladium-catalyzed pseudo-domino process is developed, in which a single Pd-based catalytic system promotes two mechanistically unrelated, sequential catalytic cycles in chronologically distinct order. Suitable precursors undergo an allylic alkylation and a Heck coupling in sequence, affording polycondensed pyrrolidone derivatives. Depending on the starting precursors, intra/inter or doubly intramolecular processes can be obtained. The allylic alkylation process takes place always very smoothly. On the other hand, the Heck coupling turns out to be rather difficult either when the process is intermolecular, or when an intramolecular process generates polycondensed structures featuring three fused bonds connected to a common carbon atom. In such difficult cases, use of the Herrmann-Beller phosphapalladacycle allowed to catalyze the coupling. This study demonstrates also that allylic alkylations can be catalyzed by the Herrmann-Beller phosphapalladacycle. 相似文献
39.
40.
Shuichi Ishida Keiki Takeda Atsushi Okamoto Ichiro Shibasaki 《Physica E: Low-dimensional Systems and Nanostructures》2004,20(3-4):255
Magnetoresistance (MR) effects have been investigated in perpendicular and parallel magnetic fields at 300, 80 K and liquid He temperatures for undoped InSb thin films 0.1–2.3 μm thick grown on GaAs(1 0 0) substrates by MBE. At high temperatures, the intrinsic carriers show the parabolic negative MR observable only in magnetic fields parallel to the film. The skipping-orbit effect due to surface boundary scattering in the classical orbits in the plane vertical to the film has been argued to be responsible for the negative MR. At low temperatures (T=80 K), the transport is dominated by the two-dimensional (2D) electrons in the accumulation layers at the InSb/GaAs(1 0 0) hetero interface; MR is positive and shows a logarithmic increase with anisotropy between parallel and perpendicular field orientation, arising from the 2D weak anti-localization (WAL) that reflects the interplay between the spin-Zeeman effect and strong spin–orbit interaction caused by the asymmetric potential at the interface (Rashba term). The zero-field spin splitting energy of Δ013 meV, the electron effective mass of m*0.10m0 seven times of the band edge mass in bulk InSb and the effective g-factor of |g*|15 in the accumulation layer have been inferred from fits of MR for the 0.1 μm thick film to the 2D WL theory. 相似文献