Polymer-protected palladium nanoparticles. Morphologies and catalytic selectivities

Colloidal palladium nanocatalysts prepared by in situ reductions of palladium chloride were immobilized and protected by either of two water-soluble polymers. The particle sizes and size distributions of the palladium colloids were determined by transmission electron microscopy. Their selectivities as catalysts were determined by comparing the extents of hydrogenation of carefully chosen pairs of small-molecule olefins. There was found to be high hydrogenation selectivity with regard to cyclic vs. noncyclic olefins. Selectivity was relatively low, however, among olefins that differed only in size (such as hexene vs. octene), or olefins differing only with regard to the positions of the double bonds (such as 1-octene vs. 3-octene). Selectivity could be improved by careful choice of the immobilizing polymer, and by its use at relatively high concentrations.     

Palladium-catalyzed reactions for the synthesis of chlorins and 5,10-porphodimethenes

The palladium-catalyzed reaction of RLi with various 5,10,15,20-tetrasubstituted porphyrins offers a convenient synthetic route to chlorins and porphodimethenes (calixphyrins). The reactions utilized various Pd catalysts and CuI and yielded either 2,3-substituted chlorins or 5,10-disubstituted porphodimethenes in yields ranging from 20-40%. The reaction of octaethylporphyrin with t-BuLi in the presence of a Pd-catalyst generated the corresponding 5,10-porphodimethene in 72% yield.     

铝镧修饰MCM-41介孔分子筛的合成、表征及在乙氧基化反应中的催化性能

以十六烷基三甲基溴化铵(CTAB)为模板剂,正硅酸乙酯(TEOS)为硅源,乙二胺为碱性介质,水热法合成了硅铝、硅镧及硅(铝 镧)摩尔比为30的Al-MCM-41、La-MCM-41和Al-La-MCM-41介孔分子筛,通过XRD、IR、NH3-TPD吸附脱附、BET、热分析及CCl4吸附等方法对分子筛的晶体结构和表面物性进行了研究,XRD及BET研究结果表明,所合成的分子筛具有典型的六方介孔结构特征及较大的比表面积.NH3-TPD结果表明所合成的介孔分子筛均达到中强酸酸度.将Al-MCM-41、La-MCM-41和Al-La-MCM-41分别用于催化乙氧基化反应,研究结果表明Al-La-MCM-41具有更高的催化活性,Al-La-MCM-41为正辛醇质量的5%,反应温度为120℃,反应压力0.2MPa,n(醇)∶n(环氧乙烷)=1∶3时,正辛醇聚氧乙烯醚产品的收率达92%.     

DFT法研究离子液中EMIM~ 催化丁烯双键异构反应机理(II)

用密度泛函理论(DFT)在B3LYP/6鄄31G(d,p)的计算水平上研究了离子液中1鄄乙基鄄3鄄甲基咪唑阳离子(EMIM )的4鄄H和5鄄H原子催化丁烯双键异构反应的可能途径,优化了反应体系的平衡态和过渡态的几何构型,分析了反应过程中键参数的变化,通过振动分析对平衡态和过渡态进行了验证.计算结果表明,离子液中的EMIM 首先通过4鄄H和5鄄H原子吸附丁烯,进而催化丁烯的双键异构反应,EMIM 的4鄄H和5鄄H催化1鄄丁烯异构为2鄄丁烯的正反应活化能分别为204.2和207.3kJ·mol-1,逆反应活化能约为220.9和223.8kJ·mol-1,反应为基元反应.     

Alkylidenverbrückte, symmetrische, zweikernige Metallocenkomplexe als Katalysatoren für die Propylenpolymerisation

The synthesis is described of symmetric alkylidene bridged dinuclear zirconocene complexes. The influence of structural parameters and different cocatalysts such as methylaluminoxane (MAO), triphenyl tetrakis(pentafluorophenyl)borate- or tris(pentafluorophenyl)borane has been investigated for homogeneous propylene polymerization. The dinuclear catalysts show highest polymerization activities by activation with MAO. Activation with triphenyl tetrakis(pentafluorophenyl)borate results in polypropylenes with the highest degree of isotacticity. Compared to the mononuclear reference catalyst the dinuclear MAO activated complex achieved higher propylene polymerization activity and the polypropylene obtained from the dinuclear complex has a higher molecular weight than that one that was produced with the mononuclear complex.     

The use of bis(diphenylphosphino)amines with N-aryl functionalities in selective ethylene tri- and tetramerisation

A systematic study was conducted on the Cr catalysed tri- and tetramerisation of ethylene using bis(diphenylphosphino)amine ligands with N-aryl functionality. This study revealed that the oligomerisation reaction product selectivity is primarily dependent on the structure and size of the N-aryl groups.

Addition of sufficient steric bulk to the N-phenyl group via ortho-alkyl substitution increased the combined 1-hexene and 1-octene selectivity (overall alpha selectivity) to above 82% at an overall 1-octene selectivity of 56%. The introduction of a single carbon spacer between the N-atom and the aryl-moiety, as well as the addition of branching on this carbon, resulted in further selectivity improvements, achieving an overall 1-octene selectivity of 64% and an overall alpha selectivity of 84%. This was obtained at catalyst productivities in excess of 1,000,000 g/g Cr/h.     

Organometallic Aspects of the Fischer-Tropsch Synthesis

The Fischer-Tropsch Synthesis counts among the industrial-scale processes having a versatile and broad product range, and has for decades offered the most attractive possibility for the use of coal as a source of heating oil and fuels. This conceivably simple reaction, the catalytic hydrogenation of carbon monoxide, generally leads to simple hydrocarbons as well (i.e. short chain olefins) that have been sought as chemical feedstocks since the oil crisis of the seventies, but fails to provide the large-scale, economic process required, due in large part to the minimal selectivity of traditional Fischer-Tropsch processes. In an effort to solve this problem current research in this sector is concerned not only with the optimization of old and the development of new catalytic systems, but also increasingly with the elucidation of numerous relevant reaction mechanisms. This article will discuss, from the viewpoint of an organometallic chemist, the significance of typical model reactions, both with regard to some fundamental aspects of synthesis gas chemistry, and in comparison with previous views concerning the mechanism of the Fischer-Tropsch Synthesis. The importance of various unique classes of complexes that have been studied in the context of Fischer-Tropsch chemistry is also evaluated with regard to their importance in the synthesis of hydrocarbons from carbon monoxide and hydrogen. It emerges that the primary steps of the reductive oligomerization of carbon monoxide are best described by the carbide/methylene mechanism, as originally proposed by Hans Fischer and Franz Tropsch.     

辅酶Ⅰ在Co／CFUE上的电化学行为及应用

辅酶I(NAD+)在0.005moL/LTris 0.01moL/LNaCl溶液(pH7.0)中,于钴离子注入修饰碳纤维电极上出现一个S形的还原波,半波电位为-1.45V(vs.SCE)。峰电流与NAD+的浓度在2.38×10-5～4.76×10-4mol/L(r=0 9992)和4.76×10-4～1.78×10-3mol/L(r=0.9982)之间成线性关系,检出限为1.19×10-5mol/L,回收率在96.7%～103.4%之间。用线性扫描、循环伏安法研究了钴离子注入修饰碳纤维电极上NAD+的电化学行为。电极反应机理为:NAD++e NAD·;NAD·+e+H+ NADH;2NAD·→NAD2。另外,钴离子注入修饰碳纤维电极对NAD+具有电催化作用。     

A novel direct synthesis of (2,2-difluorovinyl)benzenes from aromatic aldehydes

A novel catalytic approach to (2,2-difluorovinyl)benzenes has been developed. It was found that hydrazones of aromatic aldehydes generated in situ could be converted to the corresponding (2,2-difluorovinyl)benzenes by catalytic olefination reaction (COR) with dibromodifluoromethane in the presence of CuCl.     

LnSrNiO4-λ系列复合氧化物的物化性质与对NO分解的催化性能

用柠檬酸络合法合成了Ｋ２ＮｉＦ４结构的ＬｎＳｒＮｉＯ４－λ（Ｌｎ＝Ｌａ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ）系列稀土取代类钙钛石型复合氧化物催化剂，对该系列催化剂的固态物理、化学性质及其对ＮＯ分解的催化性能进行研究。结果表明，该系列复合氧化物催化剂对ＮＯ分解活性都很高，在此基础上对该系列复合氧化物中稀土元素对ＮＯ分解反应的取代效应进行了探讨。