Synthesis and crystal structure of nickel(Ⅱ) and zinc(Ⅱ) complexes with 2,4-bis(3,5-dimethylpyrazol-1-yl)-6-methoxyl-1,3,5-triazine

2,4-Bis(3,5-dimethylpyrazol-1-yl)-6-methoxyl-1,3,5-triazine(bpt) has been synthesized by using a new, simple and general method with high yields. Reactions of bpt with Ni(CIO4)2 · 6H2O and Zn(CIO4)2 · 6H2O in methanol gave mononuclear complex [Ni(bpt)2] · (CIO4)2 · H2O and ternary complex [Zn(mpt)2(dmp)](CIO4)2 respectively, where mpt (2,4-dimethoxy-6-(3,5-dimethyl-pyrazol-1-yl)-1,3,5-triazine) and dmp(3,5-dimethylpyrazole) are the alcoholysis products of bpt in the presence of Zn2+ ion. A possible mechanism for this catalytic reaction was proposed. X-ray crystal structure for ligand bpt, Ni and Zn complexes are reported. The protonated form of the ligand bpt crystallizes as its perchlorate salt including one molecule of water, [Hbpt · H2O · CIO4]. The proton is located on one pyrazole N-atom. [Hbpt ?H2O ?CIO4], in which [Hbpt]+ is in cis-cis conformation, are packed in slipped stacks of approximately parallel layers. The π-π overlap interactions between the non-protonized pyrazoles of the adjace     

负载型过渡金属氧化物催化剂上SO_2的还原

研究了γ Al2 O3负载过渡金属氧化物催化剂上CO还原SO2 的反应 ,考察了系列过渡金属对该反应的催化活性 ,发现Fe系催化剂的性能最好。同时对还原反应的条件进行了选择 ,发现在较低温度下 ,大空速不利于SO2 的还原 ,而在较高温度下 ,气体空速对反应影响不大 ,不同的物料配比对反应结果有很大影响 ,当CO∶SO2 =2时 ,最有利于单质硫生成。研究证明 ,金属硫化物是催化SO2 还原反应的活性相 ,该活性相的形成与催化剂的氧化还原能力有关 ,整个还原反应的机理应为中间产物机理     

DNA detection by dye labeled oligonucleotides using surface enhanced Raman spectroscopy

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Hypercoordinated diorganoantimony(III) compounds of types [2-(Me2NCH2)C6H4]2SbL and [PhCH2N(CH2C6H4)2]SbL (L = Cl,ONO2, OSO2CF3). Synthesis,structure and catalytic behaviour in the Henry reaction

The compounds [2-(Me₂NCH₂)C₆H₄]₂SbL (L = ONO₂ ( 2 ), OSO₂CF₃ ( 3 )) and [PhCH₂N(CH₂C₆H₄)₂]SbL (L = ONO₂ ( 5 ), OSO₂CF₃ ( 6 )) were prepared by reacting [2-(Me₂NCH₂)C₆H₄]₂SbCl ( 1 ) and [PhCH₂N(CH₂C₆H₄)₂]SbCl ( 4 ), respectively, with the appropriate silver(I) salt in a 1:1 molar ratio. The new species 2 – 6 were structurally characterized in solution using multinuclear NMR and in the solid state using infrared spectroscopy. The solid-state structures for compounds 2 , 4 and 6, as well as for the hydrolysis ionic product [{2-(Me₂N⁺HCH₂)C₆H₄}{2-(Me₂NCH₂)C₆H₄}SbOH][CF₃SO₃]⁻ ( 3h ) were determined using single-crystal X-ray diffraction. Medium to strong intramolecular N→ Sb interactions were observed in all these four compounds, thus resulting in hypercoordinated organoantimony(III) species 14-Sb-6 in 2 and 10-Sb-4 in the cation of 3h and in 4 and 6 . Compounds 1 – 6 and the starting amines PhCH₂NMe₂ and PhCH₂N(CH₂C₆H₄Br-2)₂ were investigated as catalysts in the Henry (nitroaldol) addition of nitromethane to benzaldehyde. The activity of compounds 1 – 6 resulted as an effect of the cooperation of the positively charged antimony with the negatively charged nitrogen.     

Novel aluminium compounds derived from Schiff bases: Synthesis,characterization and catalytic performance in hydroboration

Seven novel aluminium complexes supported by Schiff base ligands derived from o‐diaminobenzene or o‐aminothiophenol were synthesized and characterized. The reactions of AlMe₃ with L¹ (N,N′‐bis(benzylidine)‐o‐phenylenediamine) and L² (N,N′‐bis(2‐thienylmethylene)‐o‐phenylenediamine) gave the complexes L¹AlMe₃ ( 1 ) and L²AlMe₂ ( 2 ), respectively, which involved two types of reaction mechanisms: one was proton transfer and ring closure, and the other was alkyl transfer. Complexes L³AlMe₂ (HL³ = 4‐chlorobenzylidene‐o‐aminothiophenol) ( 3 ), L⁴AlMe₂ (HL⁴ = 2‐thiophenecarboxaldehyde‐o‐aminothiophenol) ( 4 ), L³AlH(NMe₃) ( 5 ), L⁴AlH(NMe₃) ( 6 ) and L⁵AlH(NMe₃) (HL⁵ = 4‐methylbenzylidene‐o‐aminothiophenol) ( 7 ) were prepared by reacting HL^3–5 with equimolar AlMe₃ or H₃Al?NMe₃, respectively. Compounds 3 – 7 feature an organic–inorganic hybrid containing CNAlSC five‐membered ring. All complexes were characterized using ¹H NMR and ¹³C NMR spectroscopy, X‐ray crystal structure analysis and elemental analysis. The efficient catalytic performances of 1 – 7 for the hydroboration of carbonyl groups were investigated, with compound 4 exhibiting the highest catalytic activity among all the complexes.     

稀土元素在脱硝催化剂中的应用

以NH₃为还原剂的选择性催化还原(SCR)技术可实现工业烟气中氮氧化物(NO_x)的超低排放,现有钒钛系脱硝催化剂具有生物毒性,且报废后为危险废物。稀土元素(REEs)具有独特的4f电子轨道,表现出优异的储释氧性能,在催化反应中可发挥重要作用,是当前新型脱硝催化剂的重要研究对象,也是国家鼓励的现有钒钛系催化剂的替代品。本文主要总结了铈、钐、镧等12种REEs在新型脱硝催化剂中的近5年研究进展,另有钪、镥等5种REEs的相关研究较少,重点阐述了REEs改善催化剂脱硝活性与稳定性的作用机制及耦合过渡金属的协同催化机理,初步提出了脱硝催化剂的设计原则,并展望了稀土脱硝催化剂的发展前景。     

Catalytic Light-Triggered Reduction Promoted by a Dithienylethene Derivative

A pyridinium substituted dithienylethene derivative was used for the first time as an efficient photoreducing agent of two different substrates. This reaction exhibits high catalytic yields due to the continuous regeneration of the initial state of the photochromic molecule.     

Urea-Substituted Tetramethylcyclopentadienyl Ligands for Supramolecularly Accelerated RhIII-Catalyzed ortho-C−H Olefination of Benzoic Acid Derivatives

The design and synthesis of air-stable and conveniently crystallizable Rh^III-cyclopentadienyl catalysts substituted with a urea moiety, which are able to accelerate the C−H olefination of benzoic acid derivatives, is reported. Through kinetic studies and NMR titration experiments, the catalysts’ substrate recognition ability mediated by hydrogen bonding was identified to be the reason for this effect. Introduction of pyridone-phosphine ligands capable of forming additional H-bond interactions increased the catalytic performance even further. By unveiling a proportionality between reaction rate and relative complex formation enthalpy the hypothesis of a supramolecular catalyst preformation was supported. Its application to a variety of substrates proved the catalyst system's advantages, generally increasing the yields when compared to the results obtained with widely used [RhCp*Cl₂]₂.     

Palladium-Nafion SAC-13 catalysed depolymerisation of lignin to phenols in formic acid and water

Guaiacol, pyrocatechol and resorcinol, were isolated and quantified as the major products from catalytic pyrolysis of lignin of various origin. The novel procedure utilises formic acid as the hydrogen source in combination with a palladium catalyst and Nafion^® SAC-13 as a solid acid catalyst with water as reaction medium. The reaction is conducted at moderate pyrolysis temperature and short reaction time. Several palladium based catalysts and different types of lignin were investigated. The lignins and the model compounds demonstrated various chemical behaviour, under identical reaction conditions; various phenols were formed from the lignins, while the model compounds were hydrodeoxygenated, demethylated and demethoxylated.     

Hydrodehalogenation of 4-chlorophenol and 4-bromophenol over Pd–Fe/Al2O3: influence of catalyst reduction conditions

The reduction of monometallic Pd/Al₂O₃ and bimetallic PdFe/Al₂O₃ catalysts produced by co-impregnation or sequential impregnation of the support with metal salts was possible not only under high temperature hydrogen treatment but also at 30 °C under the action of aqueous phenol solution and hydrogen. According to the XPS data, both reduction routes provided sufficient degrees of Pd reduction required for fast hydrodehalogenation of 4-chlorophenol and 4-bromophenol to phenol in aqueous solutions. The degree of Pd reduction was higher in the co-impregnated bimetallic PdFe catalyst, which was more efficient in transformation of 4-bromophenol; the bimetallic catalysts were more stable than the monometallic Pd one in the conversion of 4-chlorophenol.