Reactivities and Mechanisms for Group 14 Cation Radical Fragmentation Reactions

美国国家科学基金会化学部的化学结构、动力学和机制项目支持罗切斯特大学的Joseph Dinnocenzo教授，为14族阳离子自由基中间体的反应性和反应机制提供基本的机理见解。本研究的目的是阐明芳基三烷基硅烷、-日耳曼、-锡烷和-铅烷阳离子自由基裂解反应的机理。Dinnocenzo教授还将开发确定14组阳离子自由基亲核取代的立体化学结果的方法，并研究低聚硅烷阳离子自由基的断裂机制。这项研究的广泛影响包括为学生提供培训机会，利用轨道和键来推动有机合成研究，从而产生新的化学转化。这项工作的潜在应用在于聚硅烷光刻剂领域。本科生将通过罗切斯特大学的REU项目全年参与这项研究。丁诺森佐博士正在积极地从代表性不足的群体中招募人才。

The Chemical Structure, Dynamics and Mechanisms Program in the Chemistry Division at the National Science Foundation supports Professor Joseph Dinnocenzo of Rochester University, to provide fundamental mechanistic insight into the reactivities and reaction mechanisms of group 14 cation radical intermediates. The goal of this work is to elucidate the mechanism(s) for fragmentation reactions of aryltrialkyl-silane, -germane, -stannane, and -plumbane cation radicals. Professor Dinnocenzo will also develop methods for determining the stereochemical outcome of nucleophilic substitutions on group 14 cation radicals, and investigate the fragmentation mechanism(s) of oligosilane cation radicals.Broader impacts of the research include training opportunities for students, using orbitals and bonds to drive research in organic synthesis resulting in new chemical transformations. Potential application of this work lies in the field of polysilane photoresists. Undergraduate participation in this research will be year-round through an established REU program at the University of Rochester. Dr. Dinnocenzo is actively recruiting from underepresented groups to his laboratory.