Diastereoselective addition of lithium enolate of γ-substituted α-diazoacetoacetate to <Emphasis Type="Italic">N</Emphasis>-sulfinyl imines

Highly diastereoselective addition of lithium enolate of γ-substituted α-diazoacetoacetate to chiral N-sulfinyl imines has been developed. The addition products were further subjected to photo-induced Wolff rearrangement or Rh(II)-catalyzed intramolecular N–H insertion to afford chiral 4,5-disubstituted 2-oxo and 3-oxo pyrrolidines, respectively.     

铑催化四氢呋喃开环碘代硅基化反应研究

在四氢呋喃开环碘代硅基化反应中,一种有效的铑催化剂被首次成功应用.在该催化剂的作用下,四氢呋喃与三烷基硅烷、碘代烷烃能够顺利地发生反应并以较高的收率生成4-碘代-1-硅氧基丁烷这一重要的有机合成原料.并对反应的各实验条件也进行了优化.     

Rh纳米粒子电化学制备及其表面增强拉曼效应

利用电化学手段在氧化铟锡(ITO)导电玻璃表面成功制备了Rh纳米粒子,并发现包裹剂、支持电解质以及电化学参数对产物的形貌及尺寸有着显著影响.通过对上述参数的调控实现了Rh纳米粒子的形貌可控制备,得到了准球形、岛状以及片层状的Rh纳米粒子.此外对岛状Rh纳米粒子在表面增强拉曼光谱中的应用进行了研究.结果表明该种结构具有良好的表面增强拉曼活性.     

氧化石墨负载的手性二胺铑催化剂催化芳香酮的不对称氢转移反应

以石墨为原料通过Hummer化学氧化法制备出功能化氧化石墨材料,然后将手性二胺基团嫁接到氧化石墨上,再通过后修饰与金属铑配位制备出非均相催化剂,该催化剂在水介质中温和条件下对芳香酮的不对称氢转移反应显示出高的催化活性和对映选择活性.     

In situ time-resolved FTIR investigation on the reaction mechanism of partial oxidation of methane to syngas over supported Rh and Ru catalysts

In situ time-resolved FTIR spectroscopy was used to study the reaction mechanism of partial oxidation of methane (POM) to synthesis gas and the reaction of CH4/O2/He (2/1/45, molar ratio) gas mixture with adsorbed CO species over Rh/SiO2, Ru/γ-Al2O3 and Ru/SiO2 catalysts at 500-600℃. It was found that CO is the primary product of POM reaction over reduced and working state Rh/SiO2 catalysts. Direct oxidation of CH4 is the main pathway of synthesis gas formation over Rh/SiO2 catalyst. CO2 is the primary product of POM over Ru/γ-Al2O3 and Ru/SiO2 catalysts. The dominant reaction pathway for synthesis gas formation over Ru/γ-Al2O3 catalyst is via the reforming reactions of CH4 with CO2 and H2O. For the POM reaction over Rh/SiO2 and Ru/γ-Al2O3 catalysts, consecutive oxidation of surface CO species is an important pathway of CO2 formation.     

水-有机两相体系长链烯烃氢甲酰化反应研究--阳离子表面活性剂结构的影响

合成了四种季铵盐型阳离子表面活性剂C22H45N（CH3）2C2H5Br(二十二烷基乙基二甲基溴化铵)，C22H45N(CH3)2C4H9Br(二十二烷基丁基二甲基溴化铵)，C22H45N(CH3)2C8H17Br(二十二烷基辛基二甲基溴化铵)，C22H45N(CH3)2C12H25Br(二十二烷基十二烷基二甲基溴化铵)，并考察了其对Rh-TPPTS[TPPTS：P(m—C6H4SO3Na)3]催化的水—有机两相长链烯烃氢甲酰化反应性能的影响．研究结果表明，在该体系中添加含有疏水长链的阳离子表面活性剂后，反应性能得到明显改善．     

Half-sandwich rhodium polychalcogenide complexes and a carbon insertion into Te-Te bond

Treatment of CptRh(PMe3)Cl2(1) (Cpt = 5(- tBu2C5H3) with [Et4N]2Se6 in DMF solution leads to the formation of cyclo-tetraselenido half-sandwich rhodium complexes CptRh(PMe3)(Se4) (2). The elimination of 2 with excess of nBu3P results in cyclo-diselenido rhodium complex CptRh(PMe3)(Se2) (3). 1 reacts with [nBu4N]2Te5 in DMF solution to yield cyclo-ditellurido rhodium complex CptRh (PMe3)(Te2) (4) in which carbon atom from CH2Cl2 can be inserted into Te-Te bond to form CptRh(PMe3)(TeCH2Te) (5). The new complexes 2-5 have been characterized by their IR, EI-MS, and 1H, 13C, 31P, 103Rh NMR spectra as well as elemental analysis.     

FAAS测定汽车尾气催化剂中的铑

采用火焰原子吸收(FAAS)法对汽车尾气净化催化剂中贵金属铑(Rh)的含量进行了分析.为避免共存元素N i的谱线干扰,选择Rh的次灵敏线369.2 nm作为分析线,采用标准加入法定量、有效地消除了基体元素对测试结果的影响.催化剂样品分析相对标准偏差(RSD)为1.8%~2.7%,加标回收率为102.9%~104.7%.     

新颖手性胺基膦配体在烯胺不对称催化氢化反应中的应用

将新颖的手性胺基磷配体，6，6'－二甲氧基－2，2'－双（二苯胺基膦）－1，1'－连苯的铑铬合物应用于烯胺类化合物的不对称催化氢化反应中，发现这个铑络合物是一个有效的手性催化剂，各种手性胺产物的转化率为100％，光学选择性（ee）也达到了51％－43％。     

Rh/Ti3C2Tx MXene催化剂用于氨硼烷催化产氢

二维过渡金属碳/氮化合物基（MXene）催化剂对于水解产氢反应具有优异的催化活性.以二维过渡金属碳化钛（Ti₃C₂T_x MXene）材料为载体,采用原位还原法,制备了超高分散度的二维Ti₃C₂T_x MXene材料担载的金属铑（Rh）催化剂（Rh/Ti₃C₂T_x MXene）.利用单层二维Ti₃C₂T_x MXene材料高度暴露的表面,实现了Rh亚纳米团簇的高度分散.在常压的温和条件下,将制得的Rh/Ti₃C₂T_x MXene催化剂用于氨硼烷的常温分解.在35℃,0.1 MPa的条件下,氨硼烷可以在3 min内完全实现氢气（H₂）的释放.催化剂的结构表征证明：Rh亚纳米团簇的平均尺寸约为0.66 nm.构效关系研究表明：二维Ti₃C₂T_x MXene载体表面高度暴露的碳钛键（C-Ti）结构可以起到锚定和高度分散Rh亚纳米团簇的作用.