Identification of Organometallic Complexes for Organic Synthesis by Diffusion NMR

化学结构、动力学和机理计划支持布朗大学的Paul G.William教授，他将更好地了解重要有机金属试剂的溶液结构和反应性，同时进一步扩大扩散有序核磁共振(DOSY)方法的用途。威廉教授介绍了在理解合成化学中广泛使用的有机金属试剂聚集方面的持续发展和应用，并概述了其扩展到其他无关系统的情况，显示了该方法的范围和潜力。提出的研究包括有机锂试剂中的配体和溶剂交换过程、跨膜扩散、电池用膜的检测、混合聚集体、手性记忆效应和去质子化反应的选择性。对机理细节的考察有可能形成具有重大社会影响的新的化学转化的基础，例如药物合成、用于能源应用的新型材料和较少的负面环境影响。这项研究将开发一种重要的新方法，旨在将核磁共振光谱的使用扩展到传统的结构鉴定/结构确定的界限，进入利用这一强大的光谱技术来确定多组分混合物的尺寸和分子量参数的领域。保罗·G·威廉教授将帮助解决能源和燃料生产领域中具有国家重要性的问题。更广泛的影响包括国际合作，与市中心的公立高中合作，吸引代表不足的少数族裔本科生和研究生到他的实验室工作，与布朗大学领导力联盟计划和NSF高级计划联系。

The Chemical Structure, Dynamics and Mechanisms Program supports Professor Paul G. Williard at Brown University who will provide greater understanding of the solution structure and reactivity of important organometallic reagents while further expanding the utility of the Diffusion-Ordered NMR Spectroscopy (DOSY) method. Professor Williard describes the continued development and application of DOSY with respect to understanding aggregation of organometallic reagents used broadly in synthetic chemistry and outlines its extension to other unrelated systems showing the range and potential for the method. The research proposed includes topics such as, ligand and solvent exchange processes in organolithium reagents, diffusion across membranes, examination of membranes for battery applications, mixed aggregates, the chiral memory effect, and the selectivity of deprotonation reactions. The examination of mechanistic details has the potential to form the foundation for new chemical transformations with great societal impact, for example, drug synthesis, novel materials for energy applications and less negative environmental impact. The research will develop an important new method designed to extend the use of nuclear magnetic resonance spectroscopy beyond the traditional bounds of structure elucidation/structure determination and into the realm of utilizing this powerful spectroscopic technique to determine size and molecular weight parameters of multicomponent mixtures. Professor Paul G. Williard will help to solve problems of national importance in the realm of energy and fuel production. Broader impacts include international collaborations, working with inner city public high schools, and attracting underrepresented minority undergraduate and graduate students to work in his laboratory, liaising with the Brown University Leadership Alliance Program and the NSF ADVANCE Program.