Experiment and Computation in Physical Organic Electrochemistry

物理有机电化学实验与计算

• 批准号: 0411699
• 负责人: Albert Fry
• 金额: --
• 依托单位: Wesleyan University
• 依托单位国家: 美国
• 项目类别: Continuing grant
• 财政年份: 2004
• 资助国家: 美国
• 起止时间: 2004-07-01 至 2007-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0411699&HistoricalAwards=false
• 关键词: Experiment; Computation; Physical; Organic; Electrochemistry

With this renewal award, the Organic and Macromolecular Chemistry Program continues its support of the work of Professor Albert J. Fry of the Department of Chemistry at Wesleyan University in Middletown, CT. The research will extend the PI's investigations of physical organic electrochemistry. The anodic oxidation and the chemical reactions of organosilanes and related substances will be studied. Compounds containing silicon, which is just below carbon in the periodic table and more electropositive than carbon, readily give up an electron to a negative electrode. A second group within the same molecule such as a remote phenyl ring can assist this electron transfer. This research will explore the dimensions of this "remote effect" in order to determine what other groups facilitate electron transfer and to evaluate the possibility of replacing silicon with another element in order to discover additional synthetically useful reactions. These investigations will be complemented by computational studies aimed at developing methods for accurate estimation of the redox potentials of organic substrates and determining the nature and stereochemistry of ion-pairing and other interactions between organic cations and anions in solution. A diverse, multiracial group that includes both graduate and undergraduate students will carry out this research. The project will train students in the important areas of electrochemistry, synthesis, and computational chemistry. This research is expected to have broad positive impact on mechanistic and synthetic electrochemistry and on the development of catalysts with unique redox properties.

有了这个更新奖，有机和高分子化学计划继续支持康涅狄格州米德尔敦卫斯理大学化学系教授Albert J. Fry的工作。该研究将扩展PI的物理有机电化学研究。研究了有机硅烷和相关物质的阳极氧化和化学反应。硅元素在元素周期表中的位置仅次于碳元素，比碳元素更具正电性，因此含有硅元素的化合物很容易将一个电子传递给负极。同一分子内的第二个基团，如远程苯环，可以帮助这种电子转移。这项研究将探索这种“远程效应”的维度，以确定其他基团促进电子转移，并评估用另一种元素取代硅的可能性，以发现其他合成有用的反应。这些调查将补充计算研究，旨在开发方法，用于准确估计有机底物的氧化还原电位，并确定溶液中有机阳离子和阴离子之间的离子配对和其他相互作用的性质和立体化学。一个多元化的，多种族的群体，包括研究生和本科生将进行这项研究。该项目将培养学生在电化学，合成和计算化学的重要领域。这项研究有望对机械和合成电化学以及具有独特氧化还原性能的催化剂的开发产生广泛的积极影响。