Investigations of the Cage Effect and Aqueous Organometallic Radical Chemistry

大卫博士R.泰勒，化学系，俄勒冈州的大学，是由无机，生物无机和有机化学计划的化学部的有机金属自由基的反应性研究的支持。作为调查的一部分，笼效应，即在溶液中比在气相中更大的自由基对的反应性负责的效果，将被探测。对于质量、大小和形状不同的各种自由基对，将积累各种“笼效率因子”，即表示自由基笼对组合的效率的数字。这些数据将提供笼效应的预测性理解。该项目的第二部分涉及17-和19-电子有机金属物种在水溶液中的反应性的调查。发展了产生水溶性有机金属自由基的新方法，并使自由基的基本反应性和催化性质系统化。 化合物中的每个电子通常都是成对的. 然而，有些化合物含有一个未成对电子，这些化合物被称为自由基，它们通常具有很强的化学活性，人们越来越认识到它们参与了许多化学过程。本项目的目标是揭示控制含自由基金属化学行为的原理，并开发可溶于水的自由基。由于水是环境友好的溶剂，在水溶液中产生自由基的能力将允许通常必须在有机溶剂中进行的反应在污染较小的介质中进行。

Dr. David R. Tyler, Chemistry Department, University of Oregon, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program of the Chemistry Division for studies on the reactivity of organometallic free radicals. As one portion of the investigation the cage effect, i.e. the effect responsible for the greater reactivity of a radical pair in solution than in the gas phase, will be probed. A variety of `cage efficiency factors`, a number that expresses the efficiency of radical cage pair combinations, will be accumulated for a variety of radical pairs which differ in mass, size, and shape. These data will provide predictive understanding of the cage effect. The second part of the project involves an investigation of the reactivity of 17- and 19-electron organometallic species in aqueous solution. New methods for generating water soluble organometallic radicals will be developed and the fundamental reactivity and catalytic properties of the radicals will be systematized. Each electron in a chemical compounds is usually paired with another. However, there are some compounds which contain an unpaired electron. These are called radicals, they often are quite chemically reactive, and there is a growing realization that they are involved in many chemical processes. The object of this project is to uncover the principles which control the chemical behavior of metal containing radicals and to develop radicals which can dissolve in water. Since water is an environmentally friendly solvent, the ability to generate radicals in aqueous solutions will permit reactions which normally must be carried out in organic solvents to be performed in a less polluting medium.