稀土金属有机氢化物的合成及其引发Claisen 重排反应的研究

用(C9H7)2LnCl@2THF与过量氢化钠在THF溶液中反应,得到相应的稀土有机氢化物[(C9H7)2LnH]2@4THF@NaCl,用制得的氢化物与不饱和羰基化合物苯乙酸烯丙酯反应,发生Claisen重排,同时选择性还原羰基.     

Na(THF)2(μ2-η5-Cp)(η5,η5,η1-Cp3Yb)(THF)]n: The synthesis and X-ray structure of an anionic organolanthanidepolymer formed via self-assembly

Cp2Yb·2THF reacts with CpNa in 1：1 molar ratio in THF at 40℃ for 2 h, and the in situ generated anionic divalent complex NaYbCp3（THF）n reacts further with an excess of CpH at 40℃ for 48h, after work-up, affording the trivalent anionic ytterbium complex[Na（THF）2（μ2-η^5-Cp） （η^5, η^5,η^1-Cp3Yb）（THF）]n：（1） by oxidation reaction of Cp2Yb with CpH. Crystal structure determination reveals that complex 1 has one-dimension polymeric chains of distinct Na（THF）2（μ2-η^5-Cp） （η^5, η^5,η^1-Cp3Yb）（THF） units, which were formed by the coordination of the bridging Cp ligand with Cp3Yb＇THF and Na（THF）2 in η^5,η^5 mode via self-assembly.     

Synthesis and crystal structure of the trimetallic erbium tetrahydride complex [Li(THF)4][{(ButCp)2Er(μ-H)} 3-(μ3-H)]

Reaction of [(Bu′tCp)2Er(μ-CI)]2 with Bu′Li in 1:1 molar ratio in THF at -78℃, after work-up, afforded the trimetallic erbium tetrahydride complex [Li(THF)4][{(Bu′Cp)2Er(μ-H)}3(μ3-H)] (1) by β-hydrogen elimination reaction. Crystal structure determination reveals that complex 1 has discrete ion pair structure. The anion is composed of three (Bu′Cp)2Er units to form a triangle array connected by three bridged hydrogen atoms, and the fourth hydrogen atom coordinated to three Er^3 ions. The coordination num-ber for each Er^3 ion is 9.     

新型金属氢化物反应床传热性能分析

运用计算流体动力学（CFD）方法,对弓形折流板壳管式金属氢化物反应床进行了数值模拟.预测了反应床壳侧的流体流动状态,分析了在不同折流板数量下,反应床中壳侧的流动状态、壳侧压降和换热管内合金的温度分布.分析计算结果发现,当壳侧折流板数较多时,热流介质的流动均匀性较好,其流动死区较少,换热性能较好,壳侧压降也较大,压降损失主要存在于折流板圆缺处;增加折流板高度会有效地减少壳侧压降,并对换热性能影响很少.针对弓形折流板壳管式反应床传热性能较差,引入螺旋式折流板对反应床进行优化.结果表明,该反应床流体流动状态为旋转式,其壳侧流体的均匀性、壳侧压降以及换热管的温度分布均匀性均明显优于弓形折流板.
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Abstract：     

金属氢化物热泵特性系数的计算模型

特性系数(COP)是衡量金属氢化物热泵效率的参数。本文提出了结合实际的COP计算公式,为合理选择金属氢化物对及调整热泵的各种工艺参数提供了理论依据。计算分析表明:强化金属氢化物的传热是提高热泵效率的有效措施;热泵的工作温度存在着最佳值;适用于热泵的金属氢化物应尽可能具有平坦的平台和较小的滞后;反应器材料的比热和重量应尽可能减少以提高热泵的COP值。     

拓扑指数mZ与无机氢化物pKa1的关系

受Randic分子连接性拓扑指数的启发，构建了拓扑指数^mZ。用其1阶(^1Z)指数，1阶指数和元素电负性差的平方(XA-XH)^2与13种p区无机氢化物的pKa1值关联．拟合成2个回归方程，其相关系数与相关指数分别为0．9938和0．9961，结构选择性达到唯一性表征，预测取得了较好的结果。     

混配型茂基稀土氯化物Ln(C5H5)(C5H4CH3)Cl(Ln=Y, Gd, Er, Yb)的合成和结构研究

三氯化稀土依次与等摩尔的甲基环戊二烯基钠和环戊二烯基钠在四氢呋喃(THF)中反应，合成了4个新的混配型茂基稀土氯化物Ln(C5H5)(C5H4CH3)Cl[Ln=Y(1)，Gd(2)，Er(3)，Yb(4)]，在THF中加热回流，环戊二烯能质解化合物4的甲基环戊二烯基配体，得到同环配合物Yb(C5H5)2Cl(5)，所有这些化合物都经过了元素分析、红外和质谱表征，其中配合物2和5的结构还得到单晶X射线分析确证。     

四元镧系吸氢合金的制备与性质研究

用共沉淀还原扩散法成功地制备了新的镧系吸氢合金ＬａＮｉ４Ｃｕ１－ｘＭｎｘ（ｘ＝０．２５，０．５，０．７５），对合金进行了ＸＲＤ、ＳＥＭ、吸氢测试和热力学研究，结果表明，这些合金易活化，吸氢容量较高，其氢化物的稳定性与合金的晶胞体积之间存在线性关系，这种关系对预测氢化物稳定性有一定的指导意义。     

Low-heating solid state synthetic reactions of cyclopeantadienyl organolanthanide complexes

A novel and simple one-step,solid state reaction of multicomponent systems has been developed to synthesize cyclopentadienyl-containing organolanthanide complexes,in which the effects of the coordinated solvent molecules and the nature of the reactants were also studied.We also studied the solid state decomposition reaction of Cp2 YbPz(HPz),and the formation of [CpYb(Pz)2|2 may indicate that the constrained environment in solid state can lead to a novel chemical transformation,with product selectivity possibly different from that in the liquid phase.