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91.
P. E. M. Siegbahn 《Theoretical chemistry accounts》1994,88(6):413-424
Summary The ground state structures and bond energies have been obtained for the triatomic MHX systems where M is the entire sequence of second row transition metal atoms and X is a halide. The most interesting results of this study appear when these systems are compared to the triatomic MH2 and MX2 systems. It turns out that the structure of the MHX systems are quite similar to the corresponding MH2 systems in general. Most of the MHX systems to the right thus have bent low-spin ground states, indicating large covalent contributions to the bonding. RuHX is a special case and has a high-spin linear ground state. For the systems to the left ionicity dominates the bonding. An important result, with implications for halide ligand effects on carbonyl and olefin insertion into M-H and M-R bonds, is that the M-H bonds for the systems to the right have a different character and are significantly weaker for the MHX than for the MH2 systems. A similar effect is noted when the M-Cl bond strengths of MCl2 are compared to the ones in MHCl. Both these effects can be explained by a more cationic metal with mores
0-state character when halide ligands are present. 相似文献
92.
New Schiff bases of 2,4‐dihydroxybenzaldehyde with siloxane‐α,ω‐diamines having different numbers of siloxane units in the chain have been synthesized and characterized by spectroscopy, elemental and thermal analyses. These azomethines were found to form complexes readily with copper(II), nickel(II), cobalt(II), cadmium(II) and zinc(II). From IR and UV–Vis studies, the phenolic oxygen and imine nitrogen of the ligand were found to be the coordination sites. Thermogravimetric analysis (TGA) data indicate the chelates to be more stable than the corresponding ligands. The melting points increase with shortening of the siloxane segment from azomethine, as well as the result of complexation. The chelates obtained were covalently inserted in polymeric linear structures by polycondensation through the OH‐difunctionalized ligand with 1,3‐bis(carboxypropyl)tetramethyldisiloxane. Direct polycondensation, assisted either by acetic anhydride or N,N′‐dicyclohexylcarbodiimide as dehydrating agent and the complex 4‐(dimethylamino)pyridinium 4‐toluenesulfonate as catalyst, was used for the synthesis of these compound types. The structures of the polymers obtained were confirmed by IR, UV and 1H NMR. Characterization was undertaken by TGA, solubility tests and viscosity measurements. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
93.
研究无原子布氏代数的计算复杂性 .得到了下面的新定理 :定理 1 无原子布氏代数理论Δ具有完全的量词消去法 ,也就是说每一个式子都Δ等价于一个开式子 .定理 2 无原子布氏代数的初等型Γ (x1,… ,xn)是由型内的不含量词的全体开式子所唯一决定 .定理 3 无原子布氏代数的一个长度为 n的语句的判断过程所消耗的 Turing时间和空间都是属于 2 2 cn指数级 . 相似文献
94.
完成了19F+27Al深部非弹性碰撞产物的角分布测量.初步分析了反应产B,C,N,O,F,Ne,Na,Mg和Al的实验室系角分布,展现出深部非弹性反应机制的特点,显示了反应系统随时间的演化过程. Angular distributions of fragments produced in the deep inelastic collision of~(19)F+~(27)Al have been measured for incident energy of 114 MeV at θ_(lab)= 9~(o), 24~(o), 40~(o), 55~(o), 70~(o) and 85~(o). Angular distributions of dissipative products B, C, N, O, F, Ne, Na, Mg and Al are analyzed to provide an evolution process of the intermediate dinuclear system formed in the reaction. 相似文献
95.
Mooson Kwauk 《中国颗粒学报》2004,(1)
IntroductionInmaterialscience,differentmicrostructuresofthesamematerialsmayinducediversebehaviorsanddifferentcharacteristics.Westwood(1988)showed,asanexample,thatthetreatmentofaluminumsurfacewithcommercialphosphoricacidproducedmechanicallyinterlockedoxide搘hiskers?approximately10nmindiameterand400nminlength,whichmechanicallyinterlocked.Thismicro-structurecankeepsuchaconglomeratebondedoverconsiderablerangesofstressandtemperature.Inahumidatmosphere,especiallythatcontainingchlorine,however,suchox… 相似文献
96.
Using the full-potential linearized augmented plane wave (FP-LAPW) method, we have studied the effect of chemistry on the average intercalation voltage (AIV) caused by the Na ions intercalating into transition metal oxides. The effect of transition metal was systematically studied by varying M=Co, Ni and Mn in NaMO2 and fixing the α-NaFeO2 layered structure. The effect of the guest atoms into the host material is discussed in terms of the structural and electronic properties. Comparatively to Li intercalation, a significant electron transfer towards transition metal was found. This observation suggests that the transition metal contribute to the AIV determination and confirms the common assumption that intercalated electron reduces M4+ to M3+. 相似文献
97.
Ilaria Fratoddi Chiara Battocchio Alessandra L. Groia Maria V. Russo 《Journal of polymer science. Part A, Polymer chemistry》2007,45(15):3311-3329
The reactivity of square planar palladium(II) and platinum(II) complexes in trans or cis configuration, namely trans or cis‐[dichlorobis(tributylphosphine)platinum(II)] and trans‐[dichlorobis(tributylphosphine)palladium(II)] with 1,1′‐bis(ethynyl) 4,4′‐biphenyl, DEBP, leading to π‐conjugated organometallic oligomeric and polymeric metallaynes, was investigated by a systematic variation of the reaction conditions. The formation of polymers and oligomers with defined chain length [? M(PBu3)2 (C?C? C6H4? C6H4? C?C? )]n (n = 3–10 for the oligomers, n = 20–50 for the polymers) depends on the configuration of the precursor Pt(II) and Pd(II) complexes, the presence/absence of the catalyst CuI, and the reaction time. A series of model reactions monitored by XPS, GPC, and NMR 31P spectroscopy showed the route to modulate the chain growth. As expected, the nature of the transition metal (Pt or Pd) and the molecular weight of the polymers markedly influence the photophysical characteristics of the polymetallaynes, such as optical absorption and emission behavior. Polymetallaynes with nanostructured morphology could be obtained by a simple casting procedure of polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3311–3329, 2007 相似文献
98.
We construct a model of a shell with piezoelectric elements (patches) that take into account the mutual influence of deformations and electric fields. Coupled problems for the shell with piezoelectric patches and an acoustic field, are studied and results on the existence and the uniqueness are obtained. For this system we consider an optimal control problem on noise attenuation and obtain results on the existence, the uniqueness, necessary and sufficient conditions of optimality. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
99.
1,6-烯炔底物在过渡金属催化剂作用下的化学行为得到了广泛的研究,重点是关于过渡金属催化的1,6-烯炔环异构化反应.从反应机理角度入手,把1,6-烯炔环异构化反应按启动方式总结为三类,并对这三种方式启动的1,6-烯炔环异构化反应进行了详细地总结和阐述. 相似文献
100.