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881.
Sibrina N. Collins Constance M. Brett Bruce E. Bursten 《Journal of Cluster Science》2004,15(4):469-487
The photochemical CO-loss products of the diruthenium complexes [CpRu(CO) 2]2 (5; Cp = 5-C5H5), [Cp*Ru(CO)2]2 (5*; Cp* = 5-C5(CH3)5) and CpCp*[Ru(CO)2]2 (5) have been studied experimentally in low-temperature (96 K) matrices in 3-methylpentane by using IR spectroscopy. It is proposed that all three complexes undergo single-CO-loss chemistry but that the products have different structures. The single-CO-loss product from 5 is proposed to have one bridging and two terminal carbonyl ligands, whereas 5* and 5 generate triply bridged CO-loss products similar to that observed from [CpFe(CO)2]2 and [Cp*Fe(CO)2]2. Double-CO-loss from 5* and 5*
9 is also apparently observed. Relativistic DFT calculations have been carried out on various isomers of the starting materials and on potential CO-loss products from 5. The calculations suggest that the triply bridged product Cp2Ru2(-CO)3 (6) might have a singlet ground state in contrast to the corresponding diiron complex Cp2Fe2(-CO)3 (3), which has a triplet ground state. 相似文献
882.
Moon Hwan Cho Seung Chang Yang Nam Keun Yang Yongjin Kang Jaejung Ko 《Journal of inclusion phenomena and macrocyclic chemistry》1998,30(4):279-287
The thermodynamic parameters for the interaction of Cu2+, Ni2+, Co2+, Cd2+, andAg+ with the new title ligand have been determined by titration calorimetry in 50% THF–methanol (V/V) at 25 °C.Ag+ exhibited remarkably higher complexation selectivity.Ag+ and several transition metal ions have been transportedusing this ligand as carrier in a bulk liquid membrane. CompetitiveAg+–M2+ transport studies have also beencarried out for the same system. In this membrane transport study, high transport of Ag+ was observed in both single and competitiveAg+–M2+ transport studies. The complexformation of N,N-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (P2N2) with silver,[Ag(P2N2)] (NO3), (1) is reported. Complex 1 has been characterized by X-ray crystallography. 1 ismonoclinic, space group P21/n (No. 14), with cell dimensionsa = 13.398(4) , b=12.577(5) , c = 21.521(4) , =100.14(2) , V = 3570(2) 3 and Z = 4. 相似文献
883.
In situ polarized Fourier transform IR external reflection spectra of Langmuir monolayers of zinc stearate and zinc 12-hydroxystearate
on a water surface were recorded for various surface areas, and their molecular structures were estimated. In the zinc stearate
monolayer, the wavenumbers and the absorbances of the antisymmetric and symmetric methylene stretching bands did not change
during monolayer compression, which means that orientational and conformational changes of the hydrocarbon chain did not occur.
However, wavenumber changes of the antisymmetric and symmetric carboxylate stretching bands were observed during surface compression.
The change in the binding nature of the zinc cation to the carboxylate group was speculated. Moreover, it was elucidated that
the structure of the hydrocarbon chain in the zinc 12-hydroxystearate monolayer was different from that in the zinc stearate
monolayer.
Received: 21 March 2001 Accepted: 6 July 2001 相似文献
884.
885.
886.
石墨炉原子吸收光谱无标样分析法的研究:Ⅰ.消除基体干扰 总被引:1,自引:0,他引:1
实现石墨炉原子吸收光谱绝对分析必须消除基体干扰,本研究采用有机基体改进剂,管壁原子化、热解涂层石墨管,峰面积积分吸收信号,D2灯或Zeeman效应扣除背景,有效地控制和消除了海水基体对As,Cd,Co,Cr,Cu,Mn,Ni,Pb和V等元素的干扰,实现了无干扰测定。 相似文献
887.
本文对优化液相色谱分离条件的重叠分辨率法进行了改进与扩展:首先利用全范围的二元线性梯度淋洗进行溶剂强度的优化,再通过重叠分辨率法进行了溶剂选择性的优化,并且建立了计算机系统,使此方法程序化。利用此方法建立了分离N-二茂铁甲酰基-N'-芳基硫脲类衍生物的最佳流动相体系。 相似文献
888.
本文以多种聚醚为软段,二异氰酸酯(MDI和TDI)为硬段,合成了多嵌段聚醚聚氨酯,以此聚氨酯为基材,与NaH及1,3-丙碳酸内酯反应,进一步合成了一系列不同离子化程度的阴离子型碳化聚氨酯离聚物,用交流阻抗谱仪测定了样品的阻抗谱,由此计算出样品的离子电导率。研究结果表明其他条件相同时,以聚乙二醇(PEG)为软段的样品具有较高的离子电导率;以聚环氧丙烷(PPO)为软段的样品次之,以聚四氢呋喃(PTMO)为软段的样品最低,对于离子化程度不同的聚氨酯离聚物以金属离子和烷氧单元之比为0.05时导电性能最好。阳离子为Li+和Na+的样品具有相近的离子电导率。 相似文献
889.
CeO2—LnO1.5固溶体的表征及其甲烷催化燃烧性能 总被引:3,自引:0,他引:3
向CeO2中引入Ln3 离子后形成的CeO2-LnO1.5(Ln=La,Nd,Sm,Gd)固溶体(n(Ce):n(Ln)=1:1)是一种无贵金属的新型高效甲烷燃烧催化剂.比表面、XRD、Raman、TEM等分析证实,这类固溶体具有部分畸变的萤石结构,Ln3 进入晶格后诱发的结构变化使得团溶体的表面和本体能同时参与氧化还原反应.实验表明,该固态溶液体系是甲烷催化燃烧的良好催化剂. 相似文献
890.
Zhu XQ Cao L Liu Y Yang Y Lu JY Wang JS Cheng JP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3937-3945
Five 1-(p-substituted phenyl)-1,4-dihydronicotinamides (GPNAH-1,4-H(2)) and five 1-(p-substituted phenyl)-1,2-dihydronicotinamides (GPNAH-1,2-H(2)) were synthesized, which were used to mimic NAD(P)H coenzyme and its 1,2-dihydroisomer reductions, respectively. When the 1,4-dihydropyridine (GPNAH-1,4-H(2)) and the 1,2-dihydroisomer (GPNAH-1,2-H(2)) were treated with p-trifluoromethylbenzylidenemalononitrile (S) as a hydride acceptor, both reactions gave the same products: pyridinium derivative (GPNA(+)) and carbanion SH(-) by a hydride one-step transfer. Thermodynamic analysis on the two reactions shows that the hydride transfer from the 1,2-dihydropyridine is much more favorable than the hydride transfer from the corresponding 1,4-dihydroisomer, but the kinetic examination displays that the former reaction is remarkably slower than the latter reaction, which is mainly due to much more negative activation entropy for the former reaction. When the formed pyridinium derivative (GPNA(+)) was treated with SH(-), the major reduced product was the corresponding 1,4-dihydropyridine along with a trace of the 1,2-dihydroisomer. Thermodynamic and kinetic analyses on the hydride transfer from SH(-) to GPNA(+) all suggest that the 4-position on the pyridinium ring in GPNA(+) is much easier to accept the hydride than the 2-position, which indicates that when the 1,4-dihydropyridine is used the hydride donor to react with S, the formed pyridinium derivative GPNA(+) may return to the 1,4-dihydropyridine by a hydride transfer cycle; but when the 1,2-dihydropyridine is used as the hydride donor, the formed pyridinium derivative can not return to the 1,2-dihydropyridine by the hydride reverse transfer from SH(-) to GPNA(+). These results clearly show that the hydride-transfer cycle is favorable for the 1,4-dihydronicotinamides, but unfavorable for the corresponding 1,2-dihydroisomers. 相似文献