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11.
电离能是原子和分子的重要的特性参数,在光物理和光化学过程中起着重要作用,精确电离能对相关研究具有重要意义.电离能是调试零动能光谱信号的重要参考数据,在判断异构物数量和分子构型方面也起着关键作用.1,3-二乙氧基苯是一种重要的苯的衍生物,实验证实在超声分子束中包含两种旋转异构物Ⅰ(downup)和Ⅲ(down-down).它们的精确电离能还未见文献报道.本文采用直线式飞行时间质谱仪测量了静电场中1,3-二乙氧基苯光电离效率曲线,通过不同电场强度下测量的电离能(Stark效应)对场强的平方根线性拟合给出了两种异构物Ⅰ和Ⅲ精确的电离能分别为(62419±2)cm–1和(63378±2)cm–1.相对于通常的脉冲电场加速机制和零动能光谱测量的电离能,精确度大约分别由(±10)cm–1和(±5)cm–1提高到(±2)cm–1.分析和讨论了不同方法测量的物理机制和优缺点. 相似文献
12.
Aishabibi Kassymbek Prof. Dmitry G. Gusev Dr. Anton Dmitrienko Prof. Melanie Pilkington Prof. Georgii I. Nikonov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(4):e202103455
Reaction of the Ga(I) compound NacNacGa ( 9 ) with the diazo compound N2CHSiMe3 affords the nitrilimine compound NacNacGa(N-NCSiMe3)(CH2SiMe3) ( 10 ). Carrying out this reaction in the presence of pyridine does not lead to C−H activation on the transient alkylidene NacNacGa=CHSiMe3 but generates a metallated diazo species NacNacGa(NHN=CHSiMe3)(CN2SiMe3) ( 13 ) that further rearranges into the isonitrile compound NacNacGa(NHN=CHSiMe3)(N(NC)SiMe3) ( 15 ). Reactions of 10 with the silane H3SiPh and the borane HBcat furnished products of 1,3 addition to the nitrilimine moiety NacNacGa{N(ERn)NCSiMe3}(CH2SiMe3), whereas reaction with the diborane B2cat2 gave the product of formal nitrene insertion into the B−B bond. DFT calculations suggest that the interaction of 9 with N2CHSiMe3 proceeds through intermediate formation of an alkylidene compound that undergoes CH activation with a second molecule of N2CHSiMe3. Insertion into the B−B bond likely proceeds through an initial 1,3-addition of the diborane, followed by boryl migration to the former nitrene center. 相似文献
13.
《Journal of computational science》2014,5(4):568-575
Mechanisms for the decomposition reaction of ethylamine, CH3CH2NH2, were investigated using ab initio, DFT, and RRKM calculations. Optimized geometries of reactants, transition states, intermediates, and products were determined at HF, MP2, and B3LYP levels of theory using the 6-31G(d) and 6-31+G(d) basis sets. Single point energies were also determined at G3MP2B3 and G3B3 levels of theory. Thermodynamic properties, activation energies, enthalpies and Gibbs energies of activation were calculated for each reaction pathway investigated. Intrinsic reaction coordinate (IRC) analysis was performed to characterize the transition states on the potential energy surface. The conformational change and planarity of the ethylamine moiety along with the twist angle of the amino group about the CN axis are examined. Four pathways for the decomposition reaction of ethylamine were studied. All pathways involve a 1,2-elimination reaction and 1,3-proton shift to produce ethene, ethanimine, ethenamine, and methanimine. All pathways are single-step mechanisms. Elimination of the NH3 dominates the decomposition behavior up to 1200 K whereas after this temperature, secession of the C–N gradually holds more importance. While pathways signifying departures of NH3 and NH2 exhibit pressure-dependent behavior, branching ratios for these two channels are generally not influenced by variation in pressure higher than the atmospheric pressure. 相似文献
14.
Mark Farrell Bruno Melillo Amos B. Smith 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(1):240-243
The design, synthesis, and validation of new highly effective bifunctional linchpins for type II anion relay chemistry (ARC) has been achieved. The mechanistically novel negative‐charge migration that comprises the Brook rearrangement is now initiated by a stabilized tetrahedral intermediate, which is generated by nucleophilic addition to a Weinreb amide, rather than by a simple oxyanion that is generated from an epoxide. As a result, the linchpin preserves the carbonyl functionality in the ARC adducts, thus permitting access to functionally complex systems in a single flask without the need for further chemical manipulations. This tactic was validated with the one‐pot preparation of monoprotected 1,3‐diketones as well as pyran and spiroketal scaffolds, depending on the choice of nucleophile, electrophile, and work‐up conditions. 相似文献
15.
A general and practical synthetic method for aryl-substituted five-membered heterocycles has been developed. In the presence of KOH (30%), 1,4-diaryl-1,3-butadiynes undergo the cyclocondensation reaction with water, primary amines, and Na2S·9H2O in DMSO at 80 °C to afford 2,5-diarylfurans, 1,2,5-trisubstituted pyrroles, and 2,5-diarylthiophenes in good to high yields. Further studies have disclosed that aryl-substituted five-membered heterocycles can be also synthesized by a one-pot, two-step strategy from the terminal alkynes in DMSO firstly catalyzed by CuCl, and then via addition of KOH to promote the cyclocondensation of 1,3-butadiynes generated in situ. 相似文献
16.
Controlled dilithiation of propargyl bromide with two equivalents of n-butyllithium, in the presence of TMEDA, produces the operational equivalent of the dianion 1,3-dilithiopropyne. The latter reacts efficiently with acid chlorides to produce bishomopropargylic alcohols in a single step route and with high regioselectivity and moderate yields. 相似文献
17.
John D. Spence Miranda L. Lackie Nicola A. Clayton Sergio A. Toscano Michelle A. Farmer Esfir Popova Marilyn M. Olmstead 《Tetrahedron letters》2014
Sonogashira coupling of buta-1,3-diynylbenzene with ((2-iodophenyl)ethynyl)trimethylsilane and 1,2-diiodobenzene led to the novel enetriyne, 1-ethynyl-2-(phenylbuta-1,3-diynyl)benzene, and enetetrayne, 1,2-bis(phenylbuta-1,3-diynyl)benzene, respectively. Solid state structural and thermal analyses are also described. In solution, 1-ethynyl-2-(phenylbuta-1,3-diynyl)benzene was found to undergo thermal Bergman cyclization to afford 2-(phenylethynyl)naphthalene. 相似文献
18.
Xu Zhang Lei Zhang Meng‐Jie Wang Kou‐Lin Zhang 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(9):776-782
Two new coordination polymers (CPs) formed from 5‐iodobenzene‐1,3‐dicarboxylic acid (H2iip) in the presence of the flexible 1,4‐bis(1H‐imidazol‐1‐yl)butane (bimb) auxiliary ligand, namely poly[[μ2‐1,4‐bis(1H‐imidazol‐1‐yl)butane‐κ2N3:N3′](μ3‐5‐iodobenzene‐1,3‐dicarboxylato‐κ4O1,O1′:O3:O3′)cobalt(II)], [Co(C8H3IO4)(C10H14N4)]n or [Co(iip)(bimb)]n, (1), and poly[[[μ2‐1,4‐bis(1H‐imidazol‐1‐yl)butane‐κ2N3:N3′](μ2‐5‐iodobenzene‐1,3‐dicarboxylato‐κ2O1:O3)zinc(II)] trihydrate], {[Zn(C8H3IO4)(C10H14N4)]·3H2O}n or {[Zn(iip)(bimb)]·3H2O}n, (2), were synthesized and characterized by FT–IR spectroscopy, thermogravimetric analysis (TGA), solid‐state UV–Vis spectroscopy, single‐crystal X‐ray diffraction analysis and powder X‐ray diffraction analysis (PXRD). The iip2− ligand in (1) adopts the (κ1,κ1‐μ2)(κ1, κ1‐μ1)‐μ3 coordination mode, linking adjacent secondary building units into a ladder‐like chain. These chains are further connected by the flexible bimb ligand in a trans–trans–trans conformation. As a result, a twofold three‐dimensional interpenetrating α‐Po network is formed. Complex (2) exhibits a two‐dimensional (4,4) topological network architecture in which the iip2− ligand shows the (κ1)(κ1)‐μ2 coordination mode. The solid‐state UV–Vis spectra of (1) and (2) were investigated, together with the fluorescence properties of (2) in the solid state. 相似文献
19.
Numerical Investigation on 1,3-Butadiene/Propyne Co-pyrolysis and Insight into Synergistic Effect on Aromatic Hydrocarbon Formation 下载免费PDF全文
Tian-yu Li Jia-biao Zou Yan Zhang Chuang-chuang Cao Wei Li Wen-hao Yuan 《化学物理学报(中文版)》2017,30(3):287-294
A numerical investigation on the co-pyrolysis of 1,3-butadiene and propyne is performed to explore the synergistic effect between fuel components on aromatic hydrocarbon formation.A detailed kinetic model of 1,3-butadiene/propyne co-pyrolysis with the sub-mechanism of aromatic hydrocarbon formation is developed and validated on previous 1,3-butadiene and propyne pyrolysis experiments.The model is able to reproduce both the single component pyrolysis and the co-pyrolysis experiments,as well as the synergistic effect between 1,3-butadiene and propyne on the formation of a series of aromatic hydrocarbons.Based on the rate of production and sensitivity analyses,key reaction pathways in the fuel decomposition and aromatic hydrocarbon formation processes are revealed and insight into the synergistic effect on aromatic hydrocarbon formation is also achieved.The synergistic effect results from the interaction between 1,3-butadiene and propyne.The easily happened chain initiation in the 1,3-butadiene decomposition provides an abundant radical pool for propyne to undergo the H-atom abstraction and produce propargyl radical which plays key roles in the formation of aromatic hydrocarbons.Besides,the 1,3-butadiene/propyne co-pyrolysis includes high concentration levels of C3 and C4 precursors simultaneously,which stimulates the formation of key aromatic hydrocarbons such as toluene and naphthalene. 相似文献
20.
《Acta Crystallographica. Section C, Structural Chemistry》2017,73(7):575-581
Kryptoracemates are racemic compounds (pairs of enantiomers) that crystallize in Sohnke space groups (space groups that contain neither inversion centres nor mirror or glide planes nor rotoinversion axes). Thus, the two symmetry‐independent molecules cannot be transformed into one another by any symmetry element present in the crystal structure. Usually, the conformation of the two enantiomers is rather similar if not identical. Sometimes, the two enantiomers are related by a pseudosymmetry element, which is often a pseudocentre of inversion, because inversion symmetry is thought to be favourable for crystal packing. We obtained crystals of two kryptoracemates of two very similar compounds differing in just one residue, namely rac‐N‐[(1S ,2R ,3S )‐2‐methyl‐3‐(5‐methylfuran‐2‐yl)‐1‐phenyl‐3‐(pivalamido)propyl]benzamide, C27H32N2O3, (I), and rac‐N‐[(1S ,2S ,3R )‐2‐methyl‐3‐(5‐methylfuran‐2‐yl)‐1‐phenyl‐3‐(propionamido)propyl]benzamide dichloromethane hemisolvate, C25H28N2O3·0.5CH2Cl2, (II). The crystals of both compounds contain both enantiomers of these chiral molecules. However, since the space groups [P 212121 for (I) and P 1 for (II)] contain neither inversion centres nor mirror or glide planes nor rotoinversion axes, there are both enantiomers in the asymmetric unit, which is a rather uncommon phenomenon. In addition, it is remarkable that (II) contains two pairs of enantiomers in the asymmetric unit. In the crystal, molecules are connected by intermolecular N—H…O hydrogen bonds to form chains or layered structures. 相似文献