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Ramírez-Arizmendi LE Yu YQ Kenttämaa HI 《Journal of the American Society for Mass Spectrometry》1999,10(5):379-385
The dichlorophosphenium ion (Cl-P(+)-Cl) undergoes a variety of reactions with cyclic organic ethers in the gas phase in a Fourier-transform ion cyclotron resonance mass spectrometer. Most of the reactions are initiated by Cl-P(+)-Cl-induced heterolytic C-O bond cleavage. However, the observed final products depend on the exact structure of the ether. For saturated ethers, e.g., tetrahydropyran, tetrahydrofuran, and 2-methyltetrahydrofuran, the most abundant ionic product corresponds to hydroxide abstraction by Cl-P(+)-Cl. This unexpected reaction is rationalized by a multistep mechanism that involves an initial heterolytic C-O bond cleavage accompanied by a 1,2-hydride shift, and that ultimately yields a resonance-stabilized allyl cation and HOPCl2. The process is estimated to be highly exothermic (AM1 calculations yield delta H = -(33-38) kcal mol(-1) for the ethers mentioned above). However, the adducts formed from most of the unsaturated ethers are unable to undergo hydride shifts and hence cannot react via this pathway. In some of these cases, e.g., for 2,5-dihydrofuran and 2,5-dihydro-3,4-benzofuran, the C-O bond heterolysis is followed by oxygen/chlorine exchange to yield the O=PCl radical and a resonance-stabilized carbocation (AM1 calculations yield delta H = -14 kcal mol(-1) for the reaction of 2,5-dihydro-3,4-benzofuran). Hydride abstraction by Cl-P(+)-Cl also yields an abundant product for these two ethers. On the other hand, the ethers with low ionization energies, such as 2,3-dihydrofuran and 2,3-dihydrobenzofuran, react with Cl-P(+)-Cl by electron transfer. Finally, a unique pathway, addition followed by elimination of HCl, dominates the reaction with furan. The observed reactions are rationalized by thermochemical data obtained from semiempirical molecular orbital calculations. 相似文献
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《化学通报》2014,(6)
在B3LYP/6-31G(d,p)水平上优化了Cl原子与CH3COCH2Cl反应的各驻点的几何构型,并在相同水平上通过频率计算和内禀反应坐标(IRC)分析对过渡态的结构和反应物、产物的连接性进行了验证。采用高精确模型G3MP2方法进行单点能计算,构建了反应的势能剖面。计算结果表明,标题反应有抽氢反应、加成-消除反应、取代反应3种反应机理6条反应通道。利用经典过渡态理论(TST)和正则变分过渡态理论(CVT)计算了各反应通道在200~2000 K温度范围内的速率常数,并用小区率隧道效应模型(SCT)对抽氢反应进行校正。计算结果显示,反应有一定的变分效应,计算的总反应速率常数与文献报道的实验值符合得较好,速率常数的三参数表达式为k=2.33×10-19T2.54exp(567.07/T)cm3·mol-1·s-1。 相似文献
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在B3LYP/6-31G(d,p)水平上优化了Cl原子与CH3COCH2Cl反应的各驻点的几何构型,并在相同水平上通过频率计算和内禀反应坐标(IRC)分析对过渡态的结构和反应物、产物的连接性进行了验证。采用高精确模型G3MP2方法进行单点能计算,构建了反应的势能剖面。计算结果表明,标题反应有抽氢反应、加成-消除反应、取代反应3种反应机理6条反应通道。利用经典过渡态理论(TST)和正则变分过渡态理论(CVT)计算了各反应通道在200~2000 K温度范围内的速率常数,并用小区率隧道效应模型(SCT)对抽氢反应进行校正。计算结果显示,反应有一定的变分效应,计算的总反应速率常数与文献报道的实验值符合得较好,速率常数的三参数表达式为k=2.33×10-19T2.54exp(567.07/T)cm3·mol-1·s-1。 相似文献
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We present in this paper a time-dependent quantum wave packet calculation of the initial state selected reaction probability for H + Cl2 based on the GHNS potential energy surface with total angular momentumJ = 0. The effects of the translational, vibrational and rotational excitation of Cl2 on the reaction probability have been investigated. In a broad region of the translational energy, the rotational excitation enhances the reaction probability while the vibrational excitation depresses the reaction probability. The theoretical results agree well with the fact that it is an early down-hill reaction. 相似文献
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通过核磁共振氢谱,核磁共振碳谱,元素分析和热重分析对醚基功能化的离子液体[MOEMIm]Cl和[EOEMIm]Cl进行了表征。在温度范围T=288.15–328.15 K内,测定了离子液体[MOEMIm]Cl和[EOEMIm]Cl的密度(ρ)、表面张力(γ)和折光率(nD)。根据这些实验数据,讨论并计算了离子液体[MOEMIm]Cl和[EOEMIm]Cl的体积性质。计算出离子液体[MOEMIm]Cl和[EOEMIm]Cl的摩尔表面吉布斯自由能(gs)、摩尔表面熵(s)、摩尔表面焓(h)、摩尔极化度(Rm)和摩尔极化率(αp),h均近似为一个常数说明这两种离子液体从内部到表面的过程是一个等库仑过程,同时这两种离子液体的Rm和αp均与温度无关。本文还用摩尔表面Gibbs自由能改进Lorentz-Lorenz方程并预测离子液体表面张力,预测值与实验值高度相关。 相似文献
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纤维素在离子液体[AMMor]Cl/[AMIM]Cl混合溶剂中的溶解性能 总被引:6,自引:0,他引:6
研究了纤维素在混配离子液体N-甲基-N-烯丙基吗啉氯盐[AMMor]Cl/3-甲基-1-烯丙基咪唑氯盐[AMIM]Cl中的溶解性能, 结果表明, [AMMor]Cl/[AMIM]Cl混配溶剂能有效溶解天然纤维素, 且在相同条件下, 溶解能力要优于离子液体[AMIM]Cl; 随着溶解温度的升高, 溶解时间大大缩短. 利用FTIR, XRD和TGA方法分析了再生纤维素的化学结构和热稳定性, 结果表明, 未经活化的纤维素可直接溶于[AMMor]Cl/[AMIM]Cl而不发生其它衍生化反应, 且天然纤维素在该溶剂体系中纤维素聚合度下降较小. 相似文献
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NH4Cl的分解实验很容易与单质碘的升华现象相混淆。本方案改用恒温加热和各用酸、碱吸收剂分别检验2种气态产物,再使分解产生的2种气体相接近,观察冒白烟现象,从而使学生认识到NH4Cl受热确实发生了分解和化合反应而与碘的升华和凝华截然不同。 相似文献
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利用2种杂化的密度泛函DFT方法(BHLYP和B3LYP),2种纯DFT方法(BLYP和BP86),以DZP++为基函数对Cl2O5/Cl2O5-的平衡构型进行了量子化学计算,研究了它们的几何构型、相对能量和振动频率,并对Cl2o5/Cl2O5-体系的电子亲和势进行了理论预测. 相似文献
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L. A. Fucugauchi S. Millán A. Mondragón M. Solache-Ríos 《Journal of Radioanalytical and Nuclear Chemistry》1994,178(2):437-442
The chemical effects of98Mo(n, )99 Mo reaction on molybdenum(II) chloride [(Mo6Cl8)Cl4] have been studied. Retention, thermal and radiolytical annealing were determined. It was found that this molybdenum compound has low retention, a negligible tendency to thermal annealing and a virtual insensitivity to hydrolysis. For practical application in the enrichment of99Mo by the Shilard-Chalmers method, molybdenum(II) chloride [(Mo6Cl8)Cl4] appears to offer good prospects. 相似文献
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和强酸制弱酸,HCl NaCH3COO=NaCl CH3COOH,难溶物转化为更难溶物,AgCl NaI=NaCl AgI相同,氧化还原反应,如Cl2 2NaBr=2NaCl Br2,被氧化产物(Br2)的氧化性弱于使用的氧化剂(Cl2),被还原产物(NaCl)的还原性弱于原先的还原剂(NaBr)。显然,酸(碱)性强度、难溶的难溶程度、氧化性(还原性)倾向相差越大,以上诸反应越完全。 相似文献
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Furong Guo Dr. Chengliang Mao Chuan Liang Pan Xing Linghao Yu Dr. Yanbiao Shi Shiyu Cao Fanyu Wang Prof. Dr. Xiao Liu Prof. Dr. Zhihui Ai Prof. Dr. Lizhi Zhang 《Angewandte Chemie (International ed. in English)》2023,62(51):e202314243
BiOCl photocatalysis shows great promise for molecular oxygen activation and NO oxidation, but its selective transformation of NO to immobilized nitrate without toxic NO2 emission is still a great challenge, because of uncontrollable reaction intermediates and pathways. In this study, we demonstrate that the introduction of triangle Cl−Ag1−Cl sites on a Cl-terminated, (001) facet-exposed BiOCl can selectively promote one-electron activation of reactant molecular oxygen to intermediate superoxide radicals (⋅O2−), and also shift the adsorption configuration of product NO3− from the weak monodentate binding mode to a strong bidentate mode to avoid unfavorable photolysis. By simultaneously tuning intermediates and products, the Cl−Ag1−Cl-landen BiOCl achieved >90 % NO conversion to favorable NO3− of high selectivity (>97 %) in 10 min under visible light, with the undesired NO2 concentration below 20 ppb. Both the activity and the selectivity of Cl−Ag1−Cl sites surpass those of BiOCl surface sites (38 % NO conversion, 67 % NO3− selectivity) or control O−Ag1−O sites on a benchmark photocatalyst P25 (67 % NO conversion and 87 % NO3− selectivity). This study develops new single-atom sites for the performance enhancement of semiconductor photocatalysts, and also provides a facile pathway to manipulate the reactive oxygen species production for efficient pollutant removal. 相似文献
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The ground state structure for the CCCCCl radical was computed by using symmetry-adapted cluster configuration-interaction (SAC-CI) theory along with density functional theory to overcome the differences raised in the recently published paper [Y. Sumiyoshi et al., Chem. Phys. Lett. 414, 82 (2005)] between the theory and the experiment. SAC-CI results clearly support the earlier experimental conclusion that the radical has the bent ground state structure corresponding to 2Pi symmetry. Contrarily, probably due to spin contamination, mixing of a bent doublet ground state with the quartet components of a linear structure, coupled-cluster singles and doubles (CCSD) calculations were unable to provide reliable results. Results obtained using density functional theory also show that the radical has a bent structure. Some low-lying doublet excited states were also studied using the SAC-CI theory. The energy difference between the ground Pi state and the nearby Sigma state is around 0.2 eV. The excitation energy for the transition with the largest oscillator strength agrees with the strongest absorption peak. 相似文献