Recent advances in theoretical studies on ligand-controlled selectivity of nickel-and palladium-catalyzed cross-coupling reactions

Nickel-and palladium-catalyzed cross-coupling reactions have attracted wide attentions,while ligandcontrolled selectivity in these reactions are still elusive,and calculations can help obtain possible catalytic cycles to generate different products and provide insights into key factors of selectivity,which facilitates the development of new catalyst systems to control reaction selectivity.This review covers our efforts and some significant achievements from other groups on ligand-controlled reaction selectivity of coupling reactions,including introduction,computational methods,selectivity control by ligands in Niand Pd-catalyzed coupling reactions,as well as summary and future perspectives.     

Composites of poly(ε‐caprolactone) and Mo6S3I6 Nanowires

Composites of poly(ε‐caprolactone) (PCL) and molybdenum sulfur iodine (MoSI) nanowires were prepared using twin‐screw extrusion. Extensive microscopic examination of the composites revealed the nanowires were well dispersed in the PCL matrix, although bundles of Mo₆S₃I₆ ropes were evident at higher loadings. Secondary electron imaging (SEI) showed the nanowires had formed an extensive network throughout the PCL matrix, resulting in increased electrical conductivity of PCL, by eight orders of magnitude, and an electrical percolation threshold of 6.5 × 10^?3 vol%. Thermal analysis (DSC), WAXD, and hot stage polarized optical microscopy (HSPOM) experiments revealed Mo₆S₃I₆ addition altered PCL crystallization kinetics, nucleation density, and crystalline content. A greater number of smaller spherulites were formed via heterogeneous nucleation. The onset of thermal decomposition (TGA) of PCL decreased by 70°C, a consequence of the thermal degradation of Mo₆S₃I₆ to MoO₃, which in turn accelerates the formation of volatile gases during the first stage of PCL decomposition. Copyright © 2010 John Wiley & Sons, Ltd.     

Pd and Ni complexes of a novel vinylidene β‐diketimine ligand: Their application as catalysts in Heck coupling and alkyne trimerization

A β‐diketimine ligand with vinylidene substitution at γ‐carbon, CH₂C(CH₃CNAr)₂ (Ar = 2,6‐diisopropylphenyl) ( L ² ), was synthesized by treating β‐diketimine H₂C(CH₃CNAr)₂ with n ‐BuLi followed by paraformaldehyde. L ² formed the homobimetallic ether‐bridged β‐diketiminate complex [O{(CH₂‐β‐diketiminate)Pd(OAc)}₂] ( 1 ) with (PdOAc)₂. It also gave complexes [L²PdCl₂] ( 2 ) and [L²NiBr₂] ( 3 ) when treated with PdCl₂(CH₃CN)₂ and NiBr₂(dimethoxyethane), respectively. All the compounds were characterized using ¹H/¹³C NMR spectroscopy and single‐crystal X‐ray diffraction studies. The catalytic activity of Pd and Ni complexes 1 , 2 and 3 was explored in Heck coupling and alkyne trimerization reactions and it was found that they are very good catalysts. The results are reported in detail.     

Ni/TPC催化剂的制备、表征及在秸秆热解燃气重整中的应用

以废弃汽车外轮胎热解后的副产物轮胎热解焦（Tyre pyrolysis char，TPC）为原料，利用均匀沉淀法制备以轮胎焦为载体的负载型Ni/TPC催化剂，采用EDX、SEM、XRD、TG、BET手段对催化剂进行了表征与分析，同时使用管式炉测试了Ni/TPC催化剂在秸秆热解燃气重整中的催化性能，并考察了热解温度、保温时间、镍负载量及催化时间对秸秆热解燃气重整效果的影响。研究结果表明，TPC富含焦和金属，Ni/TPC催化剂分散均匀，热稳定性好，比表面积为62 m²/g。催化剂活性测试显示，Ni/TPC催化剂用于作物秸秆热解燃气重整具有很强的催化活性，可显著提高燃气中可燃气体含量；热解温度在750℃、保温时间10 min、30%的Ni负载量时Ni/TPC催化剂的催化效率最高，连续使用850 min后，燃气中的H₂含量仍相对提高到50%以上，长时间使用后活性结构由Ni₃ZnC_0.7转变成FeNi₃，催化活性依然较强且趋于稳定，TPC可以作为良好的新型镍基催化剂载体。     

Oxide reduced silicon nanowires

Core crystalline silicon nanowires with a heavily reduced amorphous shell have been successfully synthesised using palladium as a metal catalyst. We present two approaches to reduce the oxidation of the nanowires during the thermal annealing growth. The ratios of the amorphous shell to crystalline core of the nanowires produced, from the two methods, are compared and show a remarkable drop (hence thinner oxide) compared to wires fabricated using currently available techniques. In addition, a focused ion beam was utilised to contact the oxide-reduced nanowires for transport measurements, without first removing the thin oxide shell. The oxygen-reduced core-shell silicon nanowires showed a very low electrical resistivity (4 × 10⁻¹ Ω cm). Our novel approach presents a new alternative to the production of low cost, high yield, highly conducting silicon nanowires offering a wide range of opportunities for semiconductor based technology.     

Synthesis and optical nondestructive evaluation of GaN nanorods on silicon surfaces with gold catalyst

Nanometric gallium-nitride rods were grown on a silicon (1 1 1) substrate through a chemical vapor deposition process with gold particles as the catalyst. Randomly distributed gallium-nitride rods of 20–200 nm in diameter and of various densities and lengths were formed under different deposition conditions. Characterization analyses, such as scanning electron microscopy and optical reflection spectroscopy, have been carried out on samples containing gallium-nitride rods different in size, shape, length and density. While the scanning electron microscopy shows directly the images of the sample surfaces, the optical spectroscopy provides a nondestructive evaluation of the sample surfaces, especially helpful for checking the uniformity of the samples.