在复合体中N-异环碳联体的构造与烯转化相关
Ian C Stewart1, Diego Benitez, Daniel J O'Leary
1The Arnold and Mabel Beckman Laboratory of Chemical Synthesis and the Materials and Process Simulation Center, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
催化剂与N-多连接体显示了由于硬质因素的olefin转化中的增强反应性. 使用DFT的计算研究验证了催化剂性能和计算方法.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 计算化学计算化学
背景情况:
- 基于的催化剂对于烯转化反应至关重要.
- 了解连接体对催化剂结构和反应性的影响,是开发更高效的催化剂的关键.
- N-aryl替代剂显著影响催化剂性能.
研究的目的:
- 阐明一种基于的新型烯转化催化剂的结构和电子特性,该催化剂具有N-tolyl连接体.
- 为了将结构特征与增强的催化反应性相关联,特别是对于硬质要求高的基板.
- 使用实验数据验证密度函数理论 (DFT) 函数 (B3LYP和M06) 的准确性.
主要方法:
- 为了固态结构的确定,使用X射线晶体学.
- 溶液状态结构分析 (含有NMR光谱).
- 密度函数理论 (DFT) 计算建模.
主要成果:
- 催化剂3中的N-tolyl连接体诱导结构倾斜,在中心周围创造了更多的空间,与催化剂2中的N-mesityl连接体相比.
- 这种增加的固态可访问性与催化剂3对固态阻碍基板的增强反应性相关.
- DFT计算,特别是使用M06功能,准确地预测实验观测,B3LYP显示更接近X射线结构.
结论:
- 由N-托利连接体引入的结构修改是导致催化剂在烯转化中的反应性提高的原因.
- DFT方法是了解催化剂机制和预测性能的宝贵工具.
- 选择DFT的功能影响在预测几何和能量学中的准确性.
更多相关视频
12:19Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
10:39Heterogeneous Removal of Water-Soluble Ruthenium Olefin Metathesis Catalyst from Aqueous Media Via Host-Guest Interaction
Published on: August 23, 2018
相关概念视频
Olefin Metathesis Polymerization: Overview
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
Thermal Electrocyclic Reactions: Stereochemistry
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Criteria for Aromaticity and the Hückel 4n + 2 Rule
For the first time, Eric Hückel, a German chemical physicist, derived a set of structural features for a compound to be classified as aromatic. This is now known as Hückel’s rule or the 4n + 2 rule.
Aromatic Hydrocarbon Cations: Structural Overview
Removing one hydrogen from the intervening CH2 group with both...
