Catalytic carbonylation of potassiumN,2-dichlorobenzenesulfonamidate to sulfonyl isocyanate

Application of acetonitrile as a solvent in the catalytic carbonylation of potassiumN,2-dichlorobenzenesulfonamidate allowed to reduce the catalyst/substrate ratio and the CO pressure as compared to those used with chlorinated hydrocarbons.     

乙醇在碳修饰的二氧化钛纳米管负载的钯电催化剂上的催化氧化

 通过有机物分解碳化处理TiO2 纳米管制得了TiO2C, 并以其为载体制备了Pd/TiO2C电催化剂,考察了该催化剂对碱性介质中乙醇电催化氧化的活性. 结果表明,碳化导电处理的TiO2C纳米管载体能有效改善催化剂中贵金属的分散度和电极结构,从而提高催化剂的电催化活性. 对催化剂活性组分的优化实验表明, Pd/TiO2C质量比为1/1时催化剂的活性最高. 在1 mol/L KOH溶液中Pd载量均为0.3 mg/cm2的条件下, Pd/TiO2C催化剂对乙醇氧化的催化活性是Pd/C催化剂的3.8倍.     

Matrix separation of palladium and iridium by the cellulose anion exchanger Cellex T and the subsequent determination of palladium at theμg/g-level

The preconcentration and separation of palladium and iridium from base metals is studied with cellulose (Cellex T) and styrene-divinylbenzene (Varion AT 400) anion exchangers. In spite of lower capacity of Cellex T to chloride complexes of Pd and Ir, it allowed to get a higher preconcentration factor. Yields of 92–99% are achieved for Pd and 96–97% for Ir from the solutions containing great excess of base and heavy metals. Graphite furnace atomic absorption spectrometry is used for the final measurements. The procedure has been applied to the determination of palladium in natural samples.     

Oxidative addition of the ethane C-C bond to Pd. An ab initio benchmark and DFT validation study

We have computed a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the ethane C-C bond to the palladium atom and have used this to evaluate the performance of 24 popular density functionals, covering LDA, GGA, meta-GGA, and hybrid density functionals, for describing this reaction. The ab initio benchmark is obtained by exploring the PES using a hierarchical series of ab initio methods [HF, MP2, CCSD, CCSD(T)] in combination with a hierarchical series of five Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Our best estimate of kinetic and thermodynamic parameters is -10.8 (-11.3) kcal/mol for the formation of the reactant complex, 19.4 (17.1) kcal/mol for the activation energy relative to the separate reactants, and -4.5 (-6.8) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). Our work highlights the importance of sufficient higher angular momentum polarization functions for correctly describing metal-d-electron correlation. Best overall agreement with our ab initio benchmark is obtained by functionals from all three categories, GGA, meta-GGA, and hybrid DFT, with mean absolute errors of 1.5 to 2.5 kcal/mol and errors in activation energies ranging from -0.2 to -3.2 kcal/mol. Interestingly, the well-known BLYP functional compares very reasonably with a slight underestimation of the overall barrier by -0.9 kcal/mol. For comparison, with B3LYP we arrive at an overestimation of the overall barrier by 5.8 kcal/mol. On the other hand, B3LYP performs excellently for the central barrier (i.e., relative to the reactant complex) which it underestimates by only -0.1 kcal/mol.     

A novel palladium-catalyzed synthesis of β-carbolines: application in total synthesis of naturally occurring alkaloids

Two naturally occurring β-carbolines, 6-methoxy-2-methyl-1,2,3,4-tetrahydro-β-carboline and bauerine A, have been prepared using a Stille-type coupling, followed by a palladium-phosphine catalyzed N-heteroannulation as the key steps.     

异亚硝基乙酰乙酸乙酯亚胺Pd(Ⅱ)配合物的合成、表征和tran Pd(p-CH3C6H4-IEAI)2的晶体结构

Six palladium(Ⅱ) complexes with isonitrosoethylacetoacetate imine Schiff base ligands, Pd(R-IEAI)₂, were prepared and characterized by IR, Raman and electronic spectra. Complex tran Pd(p-CH₃C₆H₄-IEAI)₂ (2) cry- stallizes in the monoclinic system, space group P2₁/c,with a=1.2002(2),b=0.9972(2),c=1.1121(2)nm,β=90.43(3)°,Z=2,F(000)=616,μ=7.44cm^-1. The final R and wR are 0.0244 and 0.0625 for 2620 ob-served reflections with I≥2σ(I), respectively. The geometry around the Pd(Ⅱ) ions in those complexes has a distorted PdN₄ square plane, the Schiff base ligands R-IEAI^- being coordinated through their oximino-nitrogen atoms and imino-nitrogen atoms.     

Dispersion of silica nano-particles in sol-gel hybrid resins for fabrication of multi-scale hybrid nanocomposite

Multi-scale hybrid nanocomposites containing both ∼15 nm silica colloids and ∼2 nm oligosiloxanes in a methacryl polymer matrix were newly designed and fabricated. Colloidal silica sols were dispersed in methacryl oligosiloxanes nano-hybrid resins synthesized by sol-gel reaction of methacryloxypropylmethoxysilane and diphenylsilanediol. On the basis of TEM and SANS analyses, it was confirmed that the silica colloids were compatibly dispersed and different sizes of colloidal silica and oligosiloxanes co-exist in the solutions. Multi-scale hybrid nanocomposites fabricated by UV and thermal curing with incorporation of silica colloids in the nano-hybrid materials show enhanced mechanical and thermal characteristics.     

Electroreduction of Pd(II) Complexes with α-Alanine on a Palladium Electrode

The kinetics of electroreduction of Pd(II) complexes with -alanine, Pd(ala)₂, is studied on a rotating Pd disk electrode in solutions of pH 8–13 containing large excess of -alanine and various supporting electrolytes (NaF, Na₂SO₄, NaClO₄). On a Pd electrode, complexes Pd(ala)₂ undergo reduction at potentials much more negative than on an Hg electrode. This is attributed to the chemisorption of water on the Pd electrode, which hampers adsorption of Pd(ala)₂ that take part in the slow electrochemical stage. As with the Hg electrode, perchlorate ions hinder the Pd(ala)₂ reduction on a Pd electrode. Studying adsorption of Pd(ala)₂ on a Pd electrode is hampered by parallel processes of hydrogen adsorption and absorption.     

溶剂对钯催化的叔丁基乙炔低聚反应化学选择性的调控作用

报道了溶剂对钯催化的叔丁基乙炔低聚反应化学选择性的调控作用. 反应可在苯-正丁醇双组分溶剂体系中顺利进行, 当双组分溶剂体系中苯占优势比例时, 反应发生递次的三分子炔烃顺式插入, 经由顺式s-烯钯中间体生成环三聚产物1,3,5-三叔丁基苯; 而当双组分溶剂中正丁醇组分上升至一定比例, 反应选择性生成(3Z,5Z)-2,2,7,7-四甲基- 3,6-二氯-3,5-辛二烯或(3Z,5Z)-2,2,7,7-四甲基-3,6-二溴-3,5-辛二烯, 这是由于正丁醇可显著加快C—Pd σ键的断裂, 并与叔丁基乙炔、σ-烯钯中间体形成弱氢键作用力, 同时也与Pd(II)和Cu(II)等离子存在配位效应. 在强极性质子溶剂H₂O中, 反应生成偶联双炔: 2,2,7,7-四甲基-3,5-辛二炔. 文中就反应溶剂体系、钯铜催化剂及反应可能机理等分别进行了探讨.     

Polymer-supported DABCO–palladium complex as a stable and reusable catalyst for room temperature Suzuki–Miyaura cross-couplings of aryl bromides

Polymer-supported DABCO–palladium complex was observed as to be efficient and reusable catalytic system for the Suzuki–Miyaura cross-coupling reaction. In the presence of 0.25 mol % of the polymer-supported DABCO–palladium complex, a variety of aryl bromides were coupled with arylboronic acids efficiently in an aqueous ethanol at room temperature under air. Moreover, the reaction was very rapid, and the catalyst could be recovered readily from the reaction by simple filtration and could be reused at least five times.