Gas-Phase Studies of Organic Reaction Mechanisms:

有了这个更新奖，化学结构，动力学和机制计划继续支持弗吉尼亚联邦大学的斯科特·格罗内特教授在一个项目中，涉及使用质谱方法在气相中的有机反应机制的调查。这些研究将集中在两个主要领域。在第一，重要的催化剂系统将进行检查，了解他们的行动模式和开发优化其选择性的方法的目标。具体而言，金属/卡宾系统的形成和反应性将被探索，并将开发一种新的，通用的方法来筛选金属为中心的，刘易斯酸催化剂的立体选择性。在整个项目的第二个组成部分中，将探讨控制取代和消除反应的速率和选择性的因素。具体地说，取代基的亲核芳香取代反应的速率和产品的效果将被确定和消除反应的区域选择性和立体选择性的特点。对于所有这些研究，中心假设是气相反应模式通常与溶液中观察到的反应模式平行，并提供了研究该过程的替代方法。这项工作的基本原理是，通过使用气相研究，特定的，孤立的中间体的键合特性可以探测，从而获得不容易从实验中获得的机械信息，在更复杂的凝聚相环境。这些信息在未来开发使用这些反应的应用中可能是非常有价值的。 这项研究，了解气相反应模式，并显示这些将如何在溶液中观察到的一般平行，对理解许多重要的化学反应的机理途径的影响。这些研究非常适合培养本科研究人员，并有可能招募他们进入高级学位课程。外联工作将包括招募旅行到当地的学院和大学与大量的代表性不足的人口，以及直接招聘至少一名学生每年从弗吉尼亚联合大学（当地HBCU）在PI的实验室夏季研究经验。PI的研究计划传统上吸引了不同的学生群体（目前有三名来自代表性不足的群体和五名妇女），外联工作的目的是提高群体和部门的多样性。PI在过去成功地将本科生纳入有意义的研究经验，并将积极招募他们参加这些研究。

With this Renewal Award, the Chemical Structure, Dynamics, and Mechanisms Program continues to support Professor Scott Gronert of Virginia Commonwealth University in a project involving investigations of organic reaction mechanisms in the gas-phase using mass spectrometric methodologies. The studies will be focused in two major areas. In the first, important catalyst systems will be examined with goals of understanding their mode of action and developing approaches for optimizing their selectivity. Specifically, the formation and reactivity of metal/carbene systems will be explored and a new, general method for screening the stereoselectivity of metal-centered, Lewis acid catalysts will be developed. In the second component of the overall project, the factors that control the rates and the selectivities of substitution and elimination reactions will be explored. Specifically, the effect of substituent groups on the rates and products of nucleophilic aromatic substitution reactions will be determined and the regioselectivity and stereoselectivity of elimination reactions will be characterized. For all of these studies, the central hypothesis is that the gas-phase reactivity patterns will generally parallel those observed in solution and offer an alternative means of investigating the processes. The rationale for this work is that by using gas-phase studies, the bonding characteristics of specific, isolated intermediates can be probed, thus, gaining mechanistic information not readily available from experiments in the more complicated condensed phase environment. This information can be highly valuable in the future development of applications employing these reactions. This research, to understand gas phase reactivity patterns and show how these will generally parallel those observed in solution, has implications for understanding the mechanistic pathways of many important chemical reactions. These studies are ideally suited for training undergraduate researchers and potentially recruiting them into advanced degree programs. Outreach efforts will include recruiting trips to local colleges and universities with large under-represented populations as well as the direct recruiting of at least one student per year from Virginia Union University (a local HBCU) for a summer research experience in the PI's lab. The PI's research program has traditionally attracted a diverse group of students (currently three from under-represented groups and five women) and outreach efforts will be aimed at enhancing diversity in the group and the department. The PI has had success incorporating undergraduates into meaningful research experiences in the past and will actively recruit them for these studies.