Reaction Mechanisms of Heteroatomic Molecules

杂原子分子的反应机理

• 批准号: 9501282
• 负责人: Steven Bachrach
• 金额: $ 17.3万
• 依托单位: Northern Illinois University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1995
• 资助国家: 美国
• 起止时间: 1995-04-01 至 1999-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9501282&HistoricalAwards=false
• 关键词: Reaction; Mechanisms; Heteroatomic; Molecules

This grant from the Organic Dynamics Program supports the computational studies of Professor Bachrach at Northern Illinois University. The studies focus on (a) the pericyclic chemistry of thiones and thioaldehydes and (b) nucleophilic substitutions at phosphor and sulfur. The calculations will concentrate on the phospha- and thia-Claisen rearrangements, Diels-Alder reactions involving the CS double bond, the dimerization of thiaketenes, and the addition-elimination mechanism of the nucleophilic substitution at sulfur. Ab initio quantum mechanical methods at high theoretical levels will be employed to determine reaction energies, structures, and electron densities. In this computational project Dr. Bachrach will extend the theory of reaction mechanism from carbon to the heteroatoms phosphor and sulfur by an examination of pericyclic and nucleophilic substitutions. The various components of these fundamental studies will be valuable compliments to gas phase and solution work and thereby are of interest to a broad chemical audience.

有机动力学项目的资助支持了北方伊利诺伊大学Bachrach教授的计算研究。研究的重点是（a）硫酮和硫醛的周环化学和（B）磷和硫的亲核取代。计算将集中在磷-和硫-克莱森重排，涉及CS双键的Diels-Alder反应，硫杂烯酮的二聚反应，和硫的亲核取代的加成-消除机理。在高理论水平的从头算量子力学方法将被用来确定反应能量，结构和电子密度。 在这个计算项目中，Bachrach博士将通过检查周环和亲核取代，将反应机理的理论从碳扩展到杂原子磷和硫。这些基础研究的各个组成部分将是对气相和溶液工作的宝贵补充，从而引起广泛的化学受众的兴趣。