Alkaline‐Earth‐Catalysed Cross‐Dehydrocoupling of Amines and Hydrosilanes: Reactivity Trends,Scope and Mechanism

Alkaline‐earth (Ae=Ca, Sr, Ba) complexes are shown to catalyse the chemoselective cross‐dehydrocoupling (CDC) of amines and hydrosilanes. Key trends were delineated in the benchmark couplings of Ph₃SiH with pyrrolidine or tBuNH₂. Ae{E(SiMe₃)₂}₂ ? (THF)_x (E=N, CH; x=2–3) are more efficient than {N^N}Ae{E(SiMe₃)₂} ? (THF)_n (E=N, CH; n=1–2) complexes (where {N^N}^?={ArN(o‐C₆H₄)C(H)=NAr}^? with Ar=2,6‐iPr₂‐C₆H₃) bearing an iminoanilide ligand, and alkyl precatalysts are better than amido analogues. Turnover frequencies (TOFs) increase in the order Ca<Sr<Ba. Ba{CH(SiMe₃)₂}₂ ? (THF)₃ displays the best performance (TOF up to 3600 h^?1). The substrate scope (>30 products) includes diamines and di(hydrosilane)s. Kinetic analysis of the Ba‐promoted CDC of pyrrolidine and Ph₃SiH shows that 1) the kinetic law is rate=k[Ba]¹[amine]⁰[hydrosilane]¹, 2) electron‐withdrawing p‐substituents on the arylhydrosilane improve the reaction rate and 3) a maximal kinetic isotopic effect (k_SiH/k_SiD=4.7) is seen for Ph₃SiX (X=H, D). DFT calculations identified the prevailing mechanism; instead of an inaccessible σ‐bond‐breaking metathesis pathway, the CDC appears to follow a stepwise reaction path with N?Si bond‐forming nucleophilic attack of the catalytically competent Ba pyrrolide onto the incoming silane, followed by rate limiting hydrogen‐atom transfer to barium. The participation of a Ba silyl species is prevented energetically. The reactivity trend Ca<Sr<Ba results from greater accessibility of the metal centre and decreasing Ae?N_amide bond strength upon descending Group 2.     

碳酸盐法钛酸钡的研制

介绍以四氯化奂，氯化钡为原料，碳酸盐为沉淀剂，反应温度６０－８０Ｃ，反应时间３０－９０ｍｉｎ下制备碳酸钡和胶体二氧化钛相互包裹的沉淀前驱体，再经洗涤，干燥，于７５０－９５０℃下煅烧２小时得到钛酸钠粉体，讨论了工艺参数对产物纯度的影响，产物经ＸＲＤ，ＴＥＭ，能谱分析及化学分析证明为较纯的钛酸钡粉体．     

Investigation of thermal evolution of nanodomain structures in nonlinear barium sodium niobate crystals

By the 90°elastic light scattering investigation and far field observation in the range of 20-800℃,the relation between behavior of light scattering anomalies and evolution of nanodomain structures in lattice of barium sodium niobate(Ba2NaNb5O15,BSN)crystal was clarified.The correlation between anomalies on the temperature curves of the elastic light scattering intensity and temperature transformations of nanodomains was studied by X-ray and electron microscope methods.Phase transition near 500℃ and movement in field of scattering light could be explained by appearance of a new incommensurate phase.     

含BaO保护渣熔点及粘度的研究

测试了ＢａＯ－ＳｉＯ２－ＣａＯ－Ａｌ２Ｏ３（５％）－Ｎａ２Ｏ（１０％）－ＣａＦ２（１０％）六元渣系的熔点及粘度。绘出了熔点曲线图及粘度曲线图。求出了性质与化学组成的数学系式。在此基础上，提出了含ＢａＯ保护渣恰当的组成范围。     

柠檬酸溶胶凝胶法合成BaAl_(12-x)O_(19)∶Mn_x荧光粉

以AlCl3·6H2O,BaCO3和MnCO3为原料,分别溶于去离子水和柠檬酸中,采用溶胶凝胶法合成了BaAl12xO19∶Mnx荧光粉。IR分析表明,干凝胶具有柠檬酸盐结构。XRD分析表明,1200℃煅烧,粉末中的主要成分为BaAl2O4,1400℃煅烧,粉末为BaAl12xO19∶Mnx和BaAl2O4的混合物,此时仍残余部分BaAl2O4,1500℃煅烧能合成单相BaAl12xO19∶Mnx,相对于传统的高温固相合成法降低100～300℃。SEM分析表明,晶粒较小且具有片状结构。碱土金属离子Mg2+,Ca2+和Sr2+的掺杂对BaAlO∶Mn荧光粉的发光性能有一定的影响。     

复合掺杂对BaTiO3瓷介电常数温度特性的影响

研究了Ｄｙ－Ｎｂ、Ｃｅ－Ｎｂ氧化物复合掺杂对ＢａＴｉＯ３瓷温度特性的影响。结果表明，能使ＢａＴｉＯ３瓷的介电常数－温度关系曲线变得相当平缓。对造成此结果的原因，进行了理论分析和讨论。     

<Emphasis Type="Italic">In Situ</Emphasis> Synthesis of Field-responsive Nanocrystalline BaTiO<Subscript>3</Subscript> Particles Modified with Functional Organics

Nanocrystalline BaTiO₃ particles modified with polarizable ligands were synthesized through hydrolysis of modified metal–organics below 100°C. BaTiO₃ precursor was synthesized from barium metal, titanium isopropoxide and polarizable ligands in a mixture of ethanol and 2-ethoxyethanol. The modified Ba–Ti complex alkoxide was hydrolyzed yielding BaTiO₃ particles modified with organics. The crystallinty of nanometer-sized particles was dependent upon the hydrolysis conditions, and increased with increasing water amount and time. The nanocrystalline particles were identified to be BaTiO₃ by X-ray diffraction (XRD) and electron diffraction. A fluid consisting of modified BaTiO₃ particles and silicone oil revealed a typical electrorheological (ER) behavior on applying DC field. The ER behavior was found to depend upon the kind of ligand. 4-Fluorobenzyloxy modifier revealed the highest yield stress in the ER measurement among 4-substitued benzyloxy ligands examined.     

Er3+离子掺杂钡镓锗玻璃上转换发光机理研究

研究了Er³⁺离子掺杂钡镓锗玻璃的吸收光谱、拉曼光谱和上转换光谱.分析了Er³⁺离子在钡镓锗玻璃中的上转换发光机理.结果表明：玻璃的最大声子能量为828cm^-1，紫外截止波长为275nm.采用800nm和980nmLD激发玻璃样品，在室温下观察到强烈的上转换绿光和红光发射.随着Er³⁺离子浓度的增加，绿光发光强度先增加后减小，而红光发光强度呈单调递增趋势.能量分析表明：800nmLD激发产生的绿光主要源于Er³⁺离子4I_13/2能级的激发态吸收过程；红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程.980nmLD激发产生的绿光主要源于Er³⁺离子4I_11/2能级之间的能量转移过程；而红光发射主要源于Er³⁺离子4I_13/2能级与4I_11/2能级之间的能量转移过程和4I_13/2能级的激发态吸收过程.通过量子效率分析，发现采用800nmLD激发Er³⁺离子掺杂浓度为1mol% 的样品时，上转换绿光发光效率最高. 关键词： 上转换发光机理 3+离子掺杂')" href="#">Er³⁺离子掺杂 钡镓锗玻璃     

3a0．6Sr0．4TiO3／MgO／Mg2SiO4复相陶瓷的制备与介电可调性能

采用标准电子陶瓷工艺，制备了Ba0．6Sr0．4TiO3／MgO／Mg2SiO4复相陶瓷（MgO和Mg2SiO4按相同重量加入），研究了MgO和Mg2SiO4含量对复相陶瓷微观结构、介电性能及介电可调性的影响．结果表明，随着MgO和Mg2SiO4含量的增加，陶瓷的晶粒尺寸略有增大，低频（100kHz）介电常数、介电损耗、介电可调度和介电常数温度系数降低．随着偏置电场的增强，介电常数降低，介电损耗变化不大（均在10^-3量级）．当MaO和Mg2SiO4的百分含量均为30％时，获得了室温介电常数为101．6、介电损耗为0．0017及1．79kV／mm偏置电场下介电可调度为12．19％、介电常数温度系数为0．009℃^-1的介电性能。