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91.
Biing-Jiun Uang I-Pin Fu Chyuan-Der Hwang Chun-Wei Chang Chun-Tzu Yang Der-Ren Hwang 《Tetrahedron》2004,60(46):10479-10486
A highly enantioselective addition of trimethylsilylcyanide to aldehydes catalyzed by chiral titanium complexes is described. The chiral titanium complexes were prepared in situ from Ti(OiPr)4 and β-hydroxyamide ligands, that could easily be synthesized from ketopinic acid and C2 symmetrical chiral diamines in a small number of steps. 相似文献
92.
Wen-Bin Lee Shin-Chu Suen Ting-Ting Jong Fung-E Hong Jyh-Horung Chen
Hann-Jenn Lin
Lian-Pin Hwang
《Journal of organometallic chemistry》1993,450(1-2):63-66meso-Tetraphenylporphyrinatothallium(III) cyanide, Tl(tpp)(CN), was previously assumed to be monomeric and has been confirmed by X-ray analysis to exist as two independent molecules in one asymmetric unit. This unit displays two square-pyramidal coordination geometries for the thallium atoms with the cyano ligand coordinated to both Tl atoms. It crystallizes in the triclinic space group P
, with a 10.003(3), b 16.231(7), c 21.277(8) Å, 89.98(3), β 90.57(3), γ 90.31(3)°' and z = 4. The structure was solved by direct methods. A total of 7995 unique reflections having I > 3σ(I) was measured with an automated diffractometer and used to refine the crystal structure to a conventional R factor of 6.05 %. The thallium-cyanide distances are 2.140(14) Å (for thallium(I)) and 2.277(14) Å (for thallium(2)) respectively, with thallium(1) situated 0.908 Å above the porphyrin ring and thallium(2) located 1.027 Å below the ring. IR and NMR spectroscopy p rovide complementary methods for investigation of the CN ligand. The characteristic band observed at 2160 cm−1 in the FTIR spectrum is assigned to the CN stretching in the Tl(tpp)(CN) complex. The 13C resonance of axial cyano ligand is observed with a pulse delay of 3.5 s at 24°C at 139.2 ppm (with 1J(205Tl-13C) 5394 and 1J(203Tl-13C) 5344 Hz). This observation disagrees with the conclusion, drawn from previous work, in that an exchange process involving the apical ligand explains the invisibility due to line broadening at 35°C of the 13C signal. 相似文献
93.
Hwang IW Park M Ahn TK Yoon ZS Ko DM Kim D Ito F Ishibashi Y Khan SR Nagasawa Y Miyasaka H Ikeda C Takahashi R Ogawa K Satake A Kobuke Y 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(12):3753-3761
The excitation-energy-hopping (EEH) times within two-dimensional cyclic zinc(II)-porphyrin arrays 5 and 6, which were prepared by intermolecular coordination and ring-closing metathesis reaction of olefins, were deduced by modeling the EEH process based on the anisotropy depolarization as well as the exciton-exciton annihilation dynamics. Assuming the number of energy-hopping sites N = 5 and 6, the two different experimental observables, that is, anisotropy depolarization and exciton-excition annihilation times, consistently give the EEH times of 8.0 +/- 0.5 and 5.3 +/- 0.6 ps through the 1,3-phenylene linkages of 5 and 6, respectively. Accordingly, the self-assembled cyclic porphyrin arrays have proven to be well-defined two-dimensional models for natural light-harvesting complexes. 相似文献
94.
Hwang IW Kamada T Ahn TK Ko DM Nakamura T Tsuda A Osuka A Kim D 《Journal of the American Chemical Society》2004,126(49):16187-16198
meso-Pyridine-appended zinc(II) porphyrins Mn and their meso-meso-linked dimers Dn assemble spontaneously, in noncoordinating solvents such as CHCl3, into tetrameric porphyrin squares Sn and porphyrin boxes Bn, respectively. Interestingly, formation of Bn from Dn proceeds via homochiral self-sorting assembly, which has been verified by optical separations of B1 and B2. Optically pure enantiomers of B1 and B2 display strong Cotton effects in the CD spectra, which reflect the length of the pyridyl arm, thus providing evidence for the exciton coupling between the noncovalent neighboring porphyrin rings. Excitation energy migration processes within Bn have been investigated by steady-state and time-resolved spectroscopic methods in conjunction with polarization anisotropy measurements. Both the pump-power dependence on the femtosecond transient absorption and the transient absorption anisotropy decay profiles are directly associated with the excitation energy migration process within the Bn boxes, where the exciton-exciton annihilation time and the polarization anisotropy rise time are well described in terms of the F?rster-type incoherent energy hopping model by assuming a number of hopping sites of N = 4 and an exciton coherence length of L = 2. Consequently, the excitation energy hopping rates between the zinc(II) diporphyrin units have been estimated for B1 (48 ps)(-1), B2 (98 +/- 3 ps)(-1), and B3 (361 +/- 6 ps)(-1). Overall, the self-assembled porphyrin boxes Bn serve as a well-defined three-dimensional model for the light-harvesting complex. 相似文献
95.
Speciation of Cr(III) and Cr(VI) can be attained by flow injection analysis with amperometric detection. Cr(VI) is reduced in an acidic medium to Cr(III) with a glassy carbon electrode at —0.1 V vs. Ag/AgCl and the current is recorded. Cr(III) is oxidised on-line to Cr(VI) with alkaline hydrogen peroxide solution. From the difference of the total chromium and Cr(VI), the amount of Cr(III) was obtained. A linear calibration curve for Cr(VI) was obtained for the concentration ranges 0.01-5.0ppm of Cr(VI) and we have calculated the limit of determination to be about 0.5ppb. We have studied the degree of reproducibility obtained using the solid electrodes under various conditions. The influence of flow rate, coil length, interfenences and the extent of reaction were studied. 相似文献
96.
Nix and Gao established an important relation between the microindentation hardness and indentation depth. Such a relation
has been verified by many microindentation experiments (indentation depths in the micrometer range), but it does not always
hold in nanoindentation experiments (indentation depths approaching the nanometer range). Indenter tip radius effect has been
proposed by Qu et al. and others as possibly the main factor that causes the deviation from Nix and Gao's relationship. We
have developed an indentation model for micro- and nanoindentation, which accounts for two indenter shapes, a sharp, conical
indenter and a conical indenter with a spherical tip. The analysis is based on the conventional theory of mechanism-based
strain gradient plasticity established from the Taylor dislocation model to account for the effect of geometrically necessary
dislocations. The comparison between numerical result and Feng and Nix's experimental data shows that the indenter tip radius
effect indeed causes the deviation from Nix-Gao relation, but it seems not be the main factor.
The project supported by the National Natural Science Foundation of China (10121202) and the Ministry of Education of China
(20020003023) 相似文献
97.
98.
99.
Aryl pyridyl ethers were prepared from phenols and active halopyridines under essentially neutral condition via fluoride ion assisted reaction. 相似文献