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161.
Dinuclear iron(II)-cyanocarbonyl complex [PPN](2)[Fe(CN)(2)(CO)(2)(mu-SEt)](2) (1) was prepared by the reaction of [PPN][FeBr(CN)(2)(CO)(3)] and [Na][SEt] in THF at ambient temperature. Reaction of complex 1 with [PPN][SEt] produced the triply thiolate-bridged dinuclear Fe(II) complex [PPN][(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)] (2) with the torsion angle of two CN(-) groups (C(5)N(2) and C(3)N(1)) being 126.9 degrees. The extrusion of two sigma-donor CN(-) ligands from Fe(II)Fe(II) centers of complex 1 as a result of the reaction of complex 1 and [PPN][SEt] reflects the electron-rich character of the dinuclear iron(II) when ligated by the third bridging ethylthiolate. The Fe-S distances (2.338(2) and 2.320(3) A for complexes 1 and 2, respectively) do not change significantly, but the Fe(II)-Fe(II) distance contracts from 3.505 A in complex 1 to 3.073 A in complex 2. The considerably longer Fe(II)-Fe(II) distance of 3.073 A in complex 2, compared to the reported Fe-Fe distances of 2.6/2.62 A in DdHase and CpHase, was attributed to the presence of the third bridging ethylthiolate, instead of pi-accepting CO-bridged ligand as observed in [Fe] hydrogenases. Additionally, in a compound of unusual composition ([Na.(5)/(2)H(2)O][(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)])(n)((1)/(2)O(Et)(2))(n) (3), the Na(+) cations and H(2)O molecules combining with dinuclear [(CN)(CO)(2)Fe(mu-SEt)(3)Fe(CO)(2)(CN)](-) anions create a polymeric framework wherein two CN(-) ligands are coordinated via CN(-)-Na(+)/CN(-)-(Na(+))(2) linkages, respectively. 相似文献
162.
Price WJ Kuo PK Lee TR Colorado R Ying ZC Liu GY 《Langmuir : the ACS journal of surfaces and colloids》2005,21(18):8422-8428
Nanostructures of self-assembled monolayers (SAMs) are designed and produced using coadsorption and nanografting techniques. Because the structures of these artificially engineered domains are predesigned and well-characterized, a systematic investigation is possible to study the mechanical responses to force modulation under atomic force microscope tips. Force modulation imaging reveals characteristic contrast sensitivity to changes in molecular-level packing, molecule chain lengths, domain boundaries, and surface chemical functionalities in SAMs. By means of actively tuning the driving frequency, the resonances at the tip-surface contact are selectively activated. Therefore, specific surface features, such as the edges of the domains and nanostructures or desired chemical functionalities, can be selectively enhanced in the amplitude images. These observations provide a new and active approach in materials characterization and the study of nanotribology using atomic force microscopy. 相似文献
163.
Tae Oan Ahn Jung Ho Kim Jong Chan Lee Han Mo Jeong Jong-Yoon Park 《Journal of polymer science. Part A, Polymer chemistry》1993,31(2):435-441
A macro-azoinitiator containing polyarylate segment and azo group was prepared by the solution polycondensation of azobiscyanopentanoyl chloride and hydroxy-terminated polyarylates having viscosity-average molecular weights of 6200, 8100, and 12 400. These macro-azoinitiators were used in the radical polymerization of styrene to synthesize polyarylate-polystyrene block copolymers. Thermal properties measured by the differential scanning calorimetry indicated the phase separated morphology of the block copolymers except at low molecular weight of the block constituents. © 1993 John Wiley & Sons, Inc. 相似文献
164.
Meso- and dl-1,2-diarylethylenediamines (14 species) were evaluated for pre-column fluorescence derivatization reagents in the high-performance liquid chromatographic determination of catecholamines (norepinephrine, epinephrine and dopamine) in human urine and plasma. Of the compounds, meso-1,2-bis(4-methoxyphenyl)ethylenediamine was most preferable for all the catecholamines in terms of sensitivity and selectivity. The detection limit for each catecholamine is approximately 0.5 fmol in a 50-microliters injection volume. 相似文献
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A. Y. Lee 《Journal of Optimization Theory and Applications》1987,52(1):151-162
Bounded terminal conditions of nonlinear optimization problems are converted to equality terminal conditions via the Valentine's device. In so doing, additional unknown parameters are introduced into the problem. The transformed problems can still be easily solved using the sequential gradient-restoration algorithm (SGRA) via a simple augmentation of the unknown parameter vector . Three example problems with bounded terminal conditions are solved to verify this technique.This research was supported in part by the National Aeronautics and Space Administration under NASA Grant No. NCC 2-106. 相似文献
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