Structure and Rearrangements of Carbocations. The Isotopic Perturbation Method

碳阳离子的结构和重排。

• 批准号: 9006371
• 负责人: Martin Saunders
• 金额: $ 7.7万
• 依托单位: Yale University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-07-01 至 1991-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9006371&HistoricalAwards=false
• 关键词: Structure; Rearrangements; Carbocations.; Isotopic; Perturbation

In this project ("Structure and Rearrangement of Carbocations. The Isotopic Perturbation Method") in the Organic Dynamics Program, Professor Martin Saunders of the Chemistry Department at Yale University will continue studies on the development and applications of the isotopic perturbation method. The focus of this project will be the investigation of the fundamental properties of reactive carbocations. This project will be focussed on the extension of the isotopic perturbation method to study the cooperative effects of multiple deuteration which produces equilibrium isotope effects that are nonlinear functions of the number of deuterium atoms. Experimental evidence will be obtained from investigations of the angular dependence of the isotope effects in rapid processes which include rotation around single bonds that varies dihedral angles between carbocation orbitals and carbon-hydrogen and carbon-carbon bonds. Ab initio quantum mechanical calculations will be performed to predict the energies and structures of carbocations and to predict equilibrium isotope effects which will be compared with the experimental results.

在这个项目中（“碳阳离子的结构和重排。 有机动力学中的同位素微扰法 化学系的马丁·桑德斯教授 在耶鲁大学将继续研究的发展， 同位素微扰法的应用。 的焦点 这个项目将是调查的基本 活性碳阳离子的性质。 该项目将侧重于同位素的扩展 微扰法研究协同效应 产生平衡同位素效应的多重氘化 是氘原子数的非线性函数。 实验证据将从以下调查中获得： 快速同位素效应的角度依赖性 包括围绕单键旋转的过程， 改变碳阳离子轨道之间的二面角， 碳氢和碳碳键。 从头量子 将进行机械计算以预测 碳正离子的能量和结构，并预测 平衡同位素效应，将与 试验结果