Experiment and Computation in Physical Organic Electrochemistry

有机化学和高分子化学项目继续支持康涅狄格州米德尔敦卫斯理大学化学系的阿尔伯特·J·弗莱教授的工作。这项研究将扩展PI在物理有机电化学方面的研究。将研究有机硅烷及其相关物质的阳极氧化和化学反应。含有硅的化合物，在元素周期表中仅次于碳，比碳更具正电性，很容易将电子释放到负极上。同一分子中的第二个基团，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，以确定哪些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，以发现更多合成上有用的反应。这些研究将得到计算研究的补充，这些研究旨在开发准确估计有机底物的氧化还原电位的方法，并确定离子配对的性质和立体化学以及溶液中有机阳离子和阴离子之间的其他相互作用。包括研究生和本科生在内的一个多元化、多种族的群体将进行这项研究。该项目将在电化学、合成和计算化学等重要领域对学生进行培训。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。

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.