微溶剂效应对 SN2 反应动力学的影响:直接 ab initio 轨线研究

批准号:
21573052
项目类别:
面上项目
资助金额:
66.0 万元
负责人:
张家旭
依托单位:
学科分类:
B0304.化学动力学
结题年份:
2019
批准年份:
2015
项目状态:
已结题
项目参与者:
杨丽、李岩、王茗倩、胡瑒瑒、吕海屹、智美元、史雨婷
国基评审专家1V1指导 中标率高出同行96.8%
结合最新热点,提供专业选题建议
深度指导申报书撰写,确保创新可行
指导项目中标800+,快速提高中标率
微信扫码咨询
中文摘要
液相反应动力学一直是化学研究领域的重要课题。溶剂对化学反应至关重要,但目前人们对溶剂效应的认识还很不够。微溶剂化为深入研究溶剂分子影响化学反应的动力学细节提供了有效手段。SN2亲核取代反应在有机和生物化学中占有重要地位,因其简单的形式和丰富的信息成为探索复杂反应动力学的模板。本项目将使用直接 ab initio 动力学方法对微溶剂化的典型 SN2 反应 X-(H2O)n + CH3I (X = F, Cl, OH; n = 1 – 3) 开展深入系统研究,也拟将类似研究扩展到两种反应物同时溶剂化体系 X-(H2O) + CH3I(H2O)。将在原子水平上阐明微溶剂化SN2反应的特征和规律,揭示微观反应机理。结合气相动力学和相关实验,探索溶剂分子对反应进程的影响和控制机制,可望发现新机理。研究结果不仅有助于深化对SN2微溶剂动力学的理解,而且对深入认识溶剂效应和复杂的液相反应具有重要的价值。
英文摘要
The reaction dynamics in liquid phase have been an important subject. Solvents have profound influences on chemical reactions, whereas their effects remain largely unknown. Microsolvation offers an effective way to investigate the impact of solvent molecules on reaction dynamics. SN2 nucleophilic substitution reaction plays a vital role in organic chemistry and biochemistry, and has become a paradigmatic system for exploring the complicated dynamics because of its apparent simplicity and rich dynamical information. In this project, we plan to study the dynamics behaviors of typical microsolvated SN2 reactions X-(H2O)n + CH3I (X = F, Cl, OH; n = 1 – 3) by means of direct ab initio trajectory simulations. We also intend to extend the similar studies to X-(H2O) + CH3I(H2O) systems with the solvation of both reactants. It is expected that we will elaborate the characteristics and laws of these microsolvated SN2 reactions and reveal the reaction mechanisms on the atomic-level. Combined with gas phase dynamics and relevant experiments, we expect to reveal the role of solvent molecules on affecting and controlling the reactions, and hope to find new mechanisms. The findings will not only help to understand the dynamics of microsolvated SN2 reactions in detail, but also have important values in exploring solvent effects and more complicated reactions in solution.
复杂的溶液环境对人们探索液相化学反应提出了挑战。微溶剂化提供了一种有效方式调查气相到液相化学反应的变化过程,深入认识溶剂效应。我们围绕该方向,对系列水化卤交换SN2反应开展了直接动力学研究,调查体系动力学性质和规律,理解水分子的影响和作用,揭示了反应的根本特征和微观反应机理。动力学计算获得了反应截面和产物能量分配等多种微观动力学信息,与实验结果吻合。模拟进一步阐明了水分子的稳定化和位阻效应、碰撞能、冲击参数等在反应动力学中的重要作用,解释了普遍观察到的在溶剂化SN2反应中低能溶剂化产物通道受到抑制的实验现象。研究结果可为在更深的层次上理解卤交换SN2反应机理,深入认识复杂的液相反应动力学和溶剂效应提供理论基础。
期刊论文列表
专著列表
科研奖励列表
会议论文列表
专利列表
Electronic Structure Theory Study of the Microsolvated F-(H2O) + CH3I S(N)2 Reaction
微溶剂化F-(H2O)CH3I S(N)2反应的电子结构理论研究
DOI:10.1021/acs.jpca.6b00726
发表时间:2016
期刊:Journal of Physical Chemistry A
影响因子:2.9
作者:Zhang Jiaxu;Yang Li;Sheng Li
通讯作者:Sheng Li
Potential energy surface stationary points and dynamics of the F- + CH3I double inversion mechanism
F-CH3I双反演机制的势能面驻点与动力学
DOI:10.1039/c7cp02998e
发表时间:2017-08-14
期刊:PHYSICAL CHEMISTRY CHEMICAL PHYSICS
影响因子:3.3
作者:Ma, Yong-Tao;Ma, Xinyou;Hase, William L.
通讯作者:Hase, William L.
Correlation between the velocity scattering angle and product relative translational energy for S(N)2 reactions. Comparison of experiments and direct dynamics simulations
S(N)2 反应的速度散射角与产物相对平动能之间的相关性。
DOI:10.1016/j.ijms.2019.01.003
发表时间:2019
期刊:International Journal of Mass Spectrometry
影响因子:1.8
作者:Xie Jing;Zhang Jiaxu;Sun Rui;Wester Rol;Hase William L
通讯作者:Hase William L
The potential energy surface of OH anion reaction with CH3OOH: Theoretical investigations
OH阴离子与CH3OOH反应的势能面:理论研究
DOI:10.1016/j.comptc.2016.05.005
发表时间:2016
期刊:Computational and Theoretical Chemistry
影响因子:2.8
作者:Yang Li;Zhang Jiaxu
通讯作者:Zhang Jiaxu
Effect of microsolvation on the OH−(H2O)n+CH3I rate constant. comparison of experiment and calculations for OH−(H2O)2+CH3I
微溶剂化对 OH·(H2O)n CH3I 速率常数的影响。
DOI:10.1016/j.ijms.2016.10.017
发表时间:2017
期刊:International Journal of Mass Spectrometry
影响因子:1.8
作者:Jing Xie;Xinyou Ma;Jiaxu Zhang;Peter M Hierl;Albert A Viggiano;William L Hase
通讯作者:William L Hase
国内基金
海外基金
