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81.
利用IR,EXAFS, ~(13)CO同位素交换反应及与NO作用等手段研究了Pt羰基簇合物[Pt_3(CO)_6]~(2-)_n(n=3,4)在NaY分子筛超笼内的合成机理.在氧化样品Pt~(2+)/NaY上300-373 K的还愿羰基化过程中,首先Pt~(2+)与CO反应生成PtO(CO)物种(波数σ_(CO)=2110 cm~(-1)),然后聚集成“Pt_3(CO)_6”(σ_(CO)=2112,1896和1841 cm~(-1)),最后生成深绿色的Pt羰基簇合物Pt_(12)(CO)_(24)]~(2-)/NaY(σ_(CO)=2080,1824 cm~(-1)).“Pt_3(CO)_6”的羰基在室温下能迅速地与~(13)CO发生交换,而[Pt_3(CO)_6]~(2-)_n(n=3,4)的羰基与~(13)CO的同位素交换即使在343 K也进行得很慢,室温下,NO能逐步破坏Pt羰基簇合物的层间和层内Pt-Pt键,得到中间物种“Pt_3(CO)_6”和PtO(CO),同时在气相产生CO_2和N_2O.而由上述两中间物种出发,300-353 K温度下,在CO气氛中的还原羰基化又能可逆地得到原羰基簇合物. 相似文献
82.
The geometries of the most stable isomers of gold telluride systems AuTe, Au2Te, and AuTe2 are determined using the MP2 method. The aspect of gold—telluride interaction, the electron correlation, and relativistic
effects on geometry and stability are investigated at the MP2 and CCSD(T) theoretical levels. The results show that the electron
correlation and relativistic effects are responsible not only for gold—gold attraction but also for additional gold—telluride
interaction. The gold—telluride interaction is strong enough to modify the known pattern of bare gold clusters. Both effects
are essential for determining the geometry and relative stability of this type of systems. 相似文献
83.
P. R. N. De Souza D. A. G. Aranda J. W. De M. Carneiro C. Da S. B. De Oliveira O. A. C. Antunes F. B. Passos 《International journal of quantum chemistry》2003,92(4):400-411
B3 LYP hybrid functional with LACVP* pseudopotential was applied for the optimization of geometries of complexes resulting from interaction of benzene, pyridine, naphthalene, and quinoline with Ptn (n = 4, 7) clusters. For benzene‐containing complexes, the most stable form corresponds to a bridge adsorption, with benzene undergoing considerable geometric distortions, assuming a boat‐like conformation. C? H bonds are bended upward from the plane of the cluster. C? C bonds stretch, especially when they form π‐complexes with low coordinated Pt atoms. Some arrangements for pyridine complexes involving the N atom of the organic moiety undergo further distortions, apparently preserving a formal C? N π bond. Except for that distortion, the behavior of any heteroaromatic complex is similar to that of benzene in the same arrangement. The quinoline–Pt7 complex can suitably be used for simulation of the cinchonidine (CD) anchorage over Pt. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003 相似文献
84.
《中国化学快报》2020,31(5):1317-1321
Dipyrrolyldiketone difluoroboron complexes (BONEPYs) were synthesized by condensation of the corresponding pyrroles and malonyl chloride followed by treatment with BF3·OEt2. The aryl-substituted pyrrole is introduced to form a cyclic system in order to investigate anion binding studies. In BONEPYs 1–3 the o-H of the aryl group forms hydrogen bonding with F− to give a more table complex. In contrast, the intramolecular hydrogen-bonded BONEPY endo-4 is more stable than its exo isomer. While adding F−, the hydrogen bonds must be broken first to give 4·(3)F−. Owing to the electron-rich group (-OMe), the o-H of the phenyl group can hardly interact with F− via hydrogen bonding to give the less stable complex 4·(5)F−. The energy differences between the different conformations were calculated using DFT methods, which is consistent to the experimental observations. 相似文献
85.
Zareen Ahkter Andrew J. Edwards Scott L. Ingham Jack Lewis Ana M. Martin Castro Paul R. Raithby Gregory P. Shields 《Journal of Cluster Science》2000,11(1):217-226
The reaction of the di-gold cation [Au2(dppx)]2+ with the heptanuclear cluster dianion [Os7(CO)20]2– affords the mixed metal cluster [Os7(CO)20{Au2(dppx)}] (x=m (1), e (2), b (3)). On standing, in solution, this complex undergoes decarbonylation to give the cluster [Os7(CO)19{Au2(dppx)}] (x=m (4), e (5), b (6)). The complexes have been characterised spectroscopically, and an X-ray structure determination of the dppm derivative shows that it contains a metal core based on an Os7 edge-bridged bicapped tetrahedron with the two
3-Au atoms capping adjacent triangular Os3 faces of the central tetrahedron. In an analogous reaction, the carbido anion [Os7(H)C(CO)19]– affords the neutral cluster [Os7C(CO)19{Au2(dppm)}] (7) when treated with [Au2(dppm)]2+ in the presence of base. 相似文献
86.
杂合型全局优化法优化水分子团簇结构 总被引:2,自引:0,他引:2
基于遗传算法、快速模拟退火及共轭梯度方法提出了一种快速的杂合型全局优化方法(fast hybrid global optimization algorithm, FHGOA),并将这一方法应用于TIP3P和TIPS2模型水分子团簇(H2O)n结构的优化.在进行TIP3P模型水分子团簇结构的优化过程中,发现了能量比文献值更低的团簇结构,且执行效率有较大提高.把该方法应用到优化TIPS2模型的水分子团簇,发现最优结构和采用TTM2-F模型优化的水分子团簇结构在n < 17时完全相同,为全表面结构;而在n=17、19、22时为单中心水分子笼状结构;在n=25、27时为双中心水分子笼状结构.说明随着团簇中水分子个数的增加,采用TIPS2和TTM2-F势能函数优化的团簇最优结构有相同的变化趋势. 相似文献
87.
Pradeep Mathur Bala Manimaran Md. Munkir Hossain Arnold L. Rheingold Louise M. Liable-Sands Glenn P.A. Yap 《Journal of organometallic chemistry》1997,540(1-2):165-168
The tris-methylene bridged compound (NO)4Fe2Se(μ-CH2)3 has been isolated. It has been characterised by IR and 1H, 13C, and 77Se NMR spectroscopy. Its structure has been determined by single-crystal X-ray diffraction methods. The structure consists of a heavy atom triangle consisting of one Se and two Fe atoms. The Fe-Fe and the two Fe-Se edges are bridged by methylene groups. 相似文献
88.
采用乙酸乙酯为环型和线型聚苯乙烯的非良溶剂, 确定了Mark-Houwink方程分别为[η]_r=1.91×10~(-2)·M~(0.607)和[η]_l=4.06×10~(-2)·M~(0.572)。研究了环型和线型聚苯乙烯的激基缔合物的荧光效应。通过稀溶液中环型和线型高分子线团在柔顺性上存在着差异, 解释了二者之间在荧光效应方面的差异, 并根据实验结果,确定了(I_E/I_M)c→0~M关系式分别为(I_E/I_M)r,c→0=1.91+3.40×10~(-6)M和(I_E/I_M)l,c→0=2.15+3.05×10~(-6)M。 相似文献
89.
90.
纳米级金膜微电极的制作,表征及异相催化反应 总被引:1,自引:0,他引:1
报道了纳米级金膜微电极的制作方法,用XPS及SEM对电极表面进行了表征,考察了该电极的循环伏安及计时电流特性,在聚吡咯修饰微带金电极上成功地实现了葡萄糖氧化酶和电子传递媒体Fe(CN)6^3-的同时固定,并研究了GOD/Fe(CN)6^3-/PPy微酶电极对葡萄糖的响应,稳态响应电流与葡萄糖浓度之间存在Michealis-Menten动力学特征。 相似文献