潜手性Schiff碱不对称催化还原反应研究进展

对近年来潜手性Schiff碱的不对称催化氢化的发展状况按照均相、非均相及氢转移催化氢化三种类型进行了较为详尽的综述.     

Preparation of Layer Structure-Controlled Ru-Sn-Al2O3 Catalysts and Their Reactivity

In order to achieve functional group selective hydrogenation, the layer structure of Ru-Sn-Al2O3 catalysts was controlled by using sol-gel, powder impregnation and combined sol-gel impregnation methods. The properties of the catalysts and effectiveness in hydrogenation of dimethyl terephthalate were examined. The surface Sn contents of the catalysts characterized by X-ray photoelectron spectroscopy depended on the preparation method, in spite of almost the same bulk Ru and Sn compositions measured by X-ray fluorescence analyses. TPR and CO adsorption of the catalysts also depended on the preparation method. With regard to the conversion rate of dimethyl terephthalate and the rate of product conversion from methyl 4-hydroxy methylbenzoate to p-xylene via methyl p-toluate, Ru impregnation catalysts had higher rates than the other catalysts.     

Existence of finitely optimal solutions for infinite-horizon optimal control problems

In this paper, we investigate the existence of finitely optimal solutions for the Lagrange problem of optimal control defined on [0, ) under weaker convexity and seminormality hypotheses than those of previous authors. The notion of finite optimality has been introduced into the literature as the weakest of a hierarchy of types of optimality that have been defined to permit the study of Lagrange problems, arising in mathematical economics, whose cost functions either diverge or are not bounded below. Our method of proof requires us to analyze the continuous dependence of finite-interval Lagrange problems with respect to a prescribed terminal condition. Once this is done, we show that a finitely optimal solution can be obtained as the limit of a sequence of solutions to a sequence of corresponding finite-horizon optimal control problems. Our results utilize the convexity and seminormality hypotheses which are now classical in the existence theory of optimal control.This research forms part of the author's doctoral dissertation written at the University of Delaware, Newark, Delaware under the supervision of Professor Thomas S. Angell.     

Hydrogenation of fullerites in the presence of intermetallic compounds or metals

Fullerene hydrides containing 24–26 H atoms per fullerene molecule were obtained by hydrogenation of solid-phase mixtures of fullerenes with either intermetallic compounds LaNi₅, LaNi_4.65Mn_0.35, CeCo₃ or V and Pd metals with gaseous hydrogen at 1.0–2.5 MPa and 573–673 K. These fullerene hydrides decompose at 800 K with evolution of H₂. Upon subsequent heating to 1000 K, vanadium reacts with fullerene to yield a cubic phase of vanadium carbide. The intermetallic compounds react with fullerene with the formation of a metallic phase of the 3d-metal and destruction of fullerene. Palladium does not react with fullerene. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 679–683, April, 1997.     

Chiral Phosphino‐ and (Phosphinooxy)‐Substituted N‐Heterocyclic Carbene Ligands and Their Application in Iridium‐Catalyzed Asymmetric Hydrogenation

Enantiomerically pure iridium complexes with phosphino‐ and (phosphinooxy)‐substituted N‐heterocyclic carbene (NHC) ligands were synthesized. Investigation of their electronic properties showed a similar trans influence of the phosphino (or phosphinooxy) and the NHC units. The complexes were tested in iridium‐catalyzed hydrogenation. While low conversions were observed with unfunctionalized olefins, the catalysts proved to be suitable for hydrogenation of the α,β‐unsaturated ester 20 , allylic alcohol 21 , and imine 22 . The enantioselectivities were, however, moderate.     

The use of imidazolium ionic liquids for the formation and stabilization of ir0 and rh0 nanoparticles: efficient catalysts for the hydrogenation of arenes

Stable transition-metal nanoparticles of the type [M(0)](n) are easily accessible through the reduction of Ir(I) or Rh(III) compounds dissolved in "dry" 1-n-butyl-3-methylimidazolium hexafluorophosphate ionic liquid by molecular hydrogen. The formation of these [M(0)](n) nanoparticles is straightforward; they are prepared in dry ionic liquid whereas the presence of the water causes the partial decomposition of ionic liquid with the formation of phosphates, HF and transition-metal fluorides. Transmission electron microscopy (TEM) observations and X-ray diffraction analysis (XRD) show the formation of [Ir(0)](n) and [Rh(0)](n) nanoparticles with 2.0-2.5 nm in diameter. The isolated [M(0)](n) nanoparticles can be redispersed in the ionic liquid, in acetone or used in solventless conditions for the liquid-liquid biphasic, homogeneous or heterogeneous hydrogenation of arenes under mild reaction conditions (75 degrees C and 4 atm). The recovered iridium nanoparticles can be reused several times without any significant loss in catalytic activity. Unprecedented total turnover numbers (TTO) of 3509 in 32 h, for arene hydrogenation by nanoparticles catalysts, have been achieved in the reduction of benzene by the [Ir(0)](n) in solventless conditions. Contrarily, the recovered Rh(0) nanoparticles show significant agglomeration into large particles with a loss of catalytic activity. The hydrogenation of arenes containing functional groups, such as anisole, by the [Ir(0)](n) nanoparticles occurs with concomitant hydrogenolysis of the C-O bond, suggesting that these nanoparticles behave as "heterogeneous catalysts" rather than "homogeneous catalysts".     

硼掺杂还原态氧化石墨烯催化剂的制备及其蒽催化加氢性能的研究

制备了一系列硼掺杂的还原氧化态石墨烯催化剂并应用于蒽加氢反应。结果表明，随着催化剂处理温度的升高，催化剂中有序碳结构会发生变化，硼会取代材料骨架中的碳，进而影响蒽和氢气的吸附活化。经硼改性后，催化剂对蒽加氢反应表现出了很高的加氢活性，蒽的最高转化率可达97%，深度加氢产物八氢蒽的最高选择性可达19%。     

以有机镍配合物为前体制备担载镍催化剂的研究

描述了以镍单核配合物ＮｉＣｐ２和簇合物Ｎｉ３Ｃｐ３Ｎ－ｔ－Ｃ４Ｈ９为前体的ＳｉＯ２载镍催化剂的制备，通过元素分析、ＴＲＲ、ＴＰＤＥ、ＸＰＳ，ＣＯ吸附和苯加氢反应对以镍配合物和簇合物为前体制备的催化剂的性能及其制备过程了研究和表征。结果表明，镍与合物和簇合物在担载过程中同载体ＳｉＯ２表面发生了相互作用，其化学组成发生了变化，在苯加氢反应中，此催化剂的活性比以Ｎｉ（ＮＯ３）２为前体制备的催化剂高得多，