Correlating Structure and KA2 Catalytic Activity of ZnII Hydrazone Complexes

Two new Zn(II) complexes bearing tridentate hydrazone-based ligands with NNO or NNS donor atoms were synthesised and characterised by elemental analysis, infrared (IR) and nuclear magnetic resonance (NMR) spectroscopies, and single crystal X-ray diffraction methods. These complexes, together with four previously synthesised analogues, having hydrazone ligands with a NNO donor set of atoms, were successfully employed as catalysts in the ketone-amine-alkyne (KA²) coupling reaction, furnishing tetrasubstituted propargylamines, compounds with unique applications in organic chemistry. DFT calculations at the CAM-B3LYP/TZP level of theory were performed to elucidate the electronic structure of the investigated Zn(II) complexes, excellently correlating the structure of the complexes to their catalytic reactivity.     

A facile and convenient synthesis of novel imidazo[1,2-b] isoxazoles and their Mannich bases as potential biodynamic agents

A series of novel imidazo[1,2-b]isoxazoles 3 and their Mannich bases 4–6 were synthesized via convenient reactions. The reaction of 3-aminoisoxazole 1 with substituted phenacyl bromides 2 in dry ethanol afforded the corresponding 6-methyl-3-aryl imidazo[1,2-b]isoxazoles 3 in good yields.Compounds 3 on treatment with 37% formaline and secondary amines furnished the corresponding novel Mannich bases viz., 6-methyl-3-aryl-2-(morpholine/pyrrolidin-1-yl/piperidin-1-yl)-methyl-imidazo[1,2-b]isoxazoles 4–6.     

Dynamic Covalent Organocatalysts Discovered from Catalytic Systems through Rapid Deconvolution Screening

The first example of a bifunctional organocatalyst assembled through dynamic covalent chemistry (DCC) is described. The catalyst is based on reversible imine chemistry and can catalyze the Morita–Baylis–Hillman (MBH) reaction of enones with aldehydes or N‐tosyl imines. Furthermore, these dynamic catalysts were shown to be optimizable through a systemic screening approach, in which large mixtures of catalyst structures were generated, and the optimal catalyst could be directly identified by using dynamic deconvolution. This strategy allowed one‐pot synthesis and in situ evaluation of several potential catalysts without the need to separate, characterize, and purify each individual structure. The systems were furthermore shown to catalyze and re‐equilibrate their own formation through a previously unknown thiourea‐catalyzed transimination process.     

Thermal Dehydrogenation of Base‐Stabilized B2H5+ Complexes and Its Role in CH Borylation

Thermally induced dehydrogenation of the H‐bridged cation L₂B₂H₅⁺ (L=Lewis base) is proposed to be the key step in the intramolecular C? H borylation of tertiary amine boranes activated with catalytic amounts of strong “hydridophiles”. Loss of H₂ from L₂B₂H₅⁺ generates the highly reactive cation L₂B₂H₃⁺, which in its sp²‐sp³ diborane(4) form then undergoes either an intramolecular C? H insertion with B? B bond cleavage, or captures BH₃ to produce L₂B₃H₆⁺. The effect of the counterion stability on the outcome of the reaction is illustrated by formation of LBH₂C₆F₅ complexes through disproportionation of L₂B₂H₅⁺ HB(C₆F₅)₃^?.     

Different Types of Nickel,Cobalt, and Manganese Complexes originating from 2‐Imidazolecarboxaldiimine of Triethylenetetraamine

The reactivity of the 2‐imidazolecarboxaldiimine of triethylenetetraamine (H2imida) towards divalent manganese, cobalt, and nickel ions differs. It forms a cationic nickel(II) complex by acting as a hexa‐dentate ligand, whereas the cobalt(II) complex formation took place by deprotonation of the H2imida forming a neutral complex with imida. Deprotonation of the ligand by H2imida by cobalt(II) ions caused quenching of the fluorescence emission at 312 nm, such a quenching effect was not observed with the nickel ions. On the other hand, a mononuclear manganese(II) complex of a new tetradentate ligand was formed by manganese(II) assisted intramolecular cyclization reactions of H2imida.     

The PyPES library of high quality semi‐global potential energy surfaces

In this article, we present a Python‐based library of high quality semi‐global potential energy surfaces for 50 polyatomic molecules with up to six atoms. We anticipate that these surfaces will find widespread application in the testing of new potential energy surface construction algorithms and nuclear ro‐vibrational structure theories. To this end, we provide the ability to generate the energy derivatives required for Taylor series expansions to sixth order about any point on the potential energy surface in a range of common coordinate systems, including curvilinear internal, Cartesian, and normal mode coordinates. The PyPES package, along with FORTRAN, C, MATLAB and Mathematica wrappers, is available at http://sourceforge.net/projects/pypes-lib . © 2015 Wiley Periodicals, Inc.     

初中化学“酸和碱的性质”创意教学*——探析食品发热包

以食品发热包为主题情境,通过探析发热包成分、解密发热原理、计算原料配比、配制发热包等环节梳理酸和碱的性质、用途。从元素观、转化观的视角认识物质转化规律,体现物质研究的一般思路,凸显科学探究的基本过程。通过设计方案测定发热包中碳酸钠的含量,总结混合物成分鉴定及定量测定的方法;归纳气体定量测定的影响因素。呈现一堂学科观念、学科方法教学具体课例,凸显物质研究、定性检验、定量测定的基本方法。     

师范专业认证背景下无机化学课程教学改革探索*

以北京师范大学化学专业的无机化学课程改革为例,从教学内容、教学方法、课程考核等方面探讨无机化学课程优化和改革。明确教学目标,提升教学质量,达成化学(师范)专业的毕业要求,全面提升学生的思想政治素养、专业知识技能和教育情怀。     

双一流背景下有机化学精准教学的探究实践*

有机化学课程是本校化学师范和高分子材料与工程2个国家级一流本科专业以及应用化学、制药工程等专业基础必修课程。由于化学师范和非师范专业的培养目标不同,有机化学的精准教学方面也有所差异。主要从理论教学、实验教学和多媒体教学等3个方面对化学师范专业和非师范专业有机化学差异化精准教学进行了探究实践,化学师范专业有机化学的精准教学侧重于培养学生的教学能力,非师范专业有机化学的精准教学侧重于培养学生的应用能力。     

重氮化制备钯(0)催化剂及其用于合成芳香胺研究

以2,3-二氨基萘为配体,K_2PdCl_4为金属前驱体,经重氮化制备出一种Pd(0)纳米催化剂(Pd-NPs),其结构经TEM、 XPS、 XRD、 EA和ICP-OES表征,并将催化剂应用于芳香醛类化合物直接还原胺化反应中.在常温常压下以苯甲醛为底物,水为溶剂,H_2为还原剂,探究了胺源、溶剂pH、催化剂用量、反应时间等变量对芳香伯胺产率的影响.实验结果表明芳香伯胺产率高达99%,且该催化剂能多次使用而不失活.