Theoretical Studies of Main Group Organometallic Chemistry

主族金属有机化学理论研究

• 批准号: 9633480
• 负责人: Mark Gordon
• 金额: $ 26.61万
• 依托单位: Iowa State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1997
• 资助国家: 美国
• 起止时间: 1997-01-01 至 2001-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9633480&HistoricalAwards=false
• 关键词: Theoretical; Studies; Main; Group; Organometallic

The Theoretical and Computational Chemistry Program is supporting Prof. Mark Gordon of Iowa State University. The research to be performed will be a combination of theory and code development in quantum chemistry and related areas and applications of modern quantum chemistry to problems in main group organometallic chemistry. The new developments in theory will focus on two areas: (1) an extension of the effective fragment method for solvation to any solvent, to excited states, and to include higher-order intermolecular interactions, and (2) to extend the interface between quantum chemistry and dynamics to facilitate the study of dynamics of liquids and solvation dynamics. One of the key applications areas interfaces with these new theory developments, namely the study of the influence of solvation on mechanisms in organometallic chemistry. Among the many mechanisms of interest are the nature of the ring opening in cyclic organosilicon compounds, the effect of catalysts on reactions such as the hydrosilation and bis-silylation reactions, and the nature of the organometallic coupling reaction. Other applications include a broad-based study of the chemistry of titanium and other Group IVB elements, and quantitative studies of the thermochemistry of main group- transition metal bonding. Although most chemical reactions occur in the presence of a solvent, until very recently, the vast majority of theoretical studies have been carried out on isolated molecules. Even now, most current models that include the effects of solvents do not explicitly treat the individual solvent molecules and therefore cannot determine the nature of the interactions between the chemical system of interest and the solvent. The Gordon group has developed a new solvent model, the effective fragment potential model, that is designed to treat the solvent molecules explicitly. Currently, this model is limited to the most ubiquitous solvent, water. This model will now be extended so that any solvent of interest in organometallic chemistry will be accessible. The new method will be applied to study the effects of solvation on several important chemical reactions. It is anticipated that these studies will provide some fundamental understanding of how these reactions occur and ultimately provide some guidance on the design of new products.

理论和计算化学计划支持爱荷华州州立大学的Mark Gordon教授。 将要进行的研究将是量子化学和相关领域的理论和代码开发的结合，以及现代量子化学在主族有机金属化学问题中的应用。 理论上的新发展将集中在两个领域：（1）将溶剂化的有效碎片方法扩展到任何溶剂，激发态，并包括高阶分子间相互作用，以及（2）扩展量子化学和动力学之间的界面，以促进液体动力学和溶剂化动力学的研究。 其中一个关键的应用领域接口与这些新的理论发展，即在有机金属化学的溶剂化机制的影响的研究。 在许多感兴趣的机理中，有环状有机硅化合物中开环的性质、催化剂对诸如硅氢化和双甲硅烷基化反应的反应的影响以及有机金属偶联反应的性质。 其他应用包括 对钛和其他IVB族元素化学的广泛研究，以及对主族过渡的热化学的定量研究 金属键合 虽然大多数化学反应都是在溶剂存在下进行的， 直到最近，绝大多数的理论研究都是在 在孤立的分子上。 即使是现在，大多数当前的模型，包括 溶剂的效应没有明确地处理单个溶剂分子，因此不能确定感兴趣的化学体系和溶剂之间的相互作用的性质。 戈登小组发展了一种新的溶剂模型，有效碎片势模型， 专门用来处理溶剂分子的 目前，该模型仅限于最普遍的溶剂水。 这个模型现在将被扩展，使任何感兴趣的有机金属溶剂， 化学将是可访问的。 新方法将被应用于研究效果 在几个重要的化学反应中的作用。 预计 这些研究将为这些反应如何发生提供一些基本的理解，并最终为新产品的设计提供一些指导。