RII Track 4: Electronic Structure Calculations to Characterize Mechanisms of Regioselective Additions to Olefins and to Advance P-31 NMR as a Reporter of Catalytic Intermediates

非技术描述金属和有机化合物之间的化学反应可能是复杂的，反应过程中通常有许多步骤。需要更好地了解这些反应涉及的机理和潜在的分子结构，以优化过程和预测这些工业上重要的反应可能产生的分子结构。PI将在伊利诺伊大学香槟分校(UIUC)进行研究，她和她的合作者将专注于反应，如用于合成候选药物和药物的反应。UIUC国家超级计算应用中心的可用资源将用于开展基于PI计算化学背景的工作。UIUC的计算能力和先进的化学分析仪器的可用性将对解开正在研究的反应机理具有重要价值。除了能够使用这些设施外，国际和平协会和她来自威奇托州立大学的学生将与UIUC一个活跃的研究小组形成密切合作，从而加强两个机构之间的伙伴关系。该研究金将支持PI在UIUC的活动，以计算表征区域选择性的烯烃加成反应，催化的是Rh和Ir膦络合物。协同计算-实验将开发一个框架来指导合成进展。电子结构计算将被用来获得有机金属配合物、催化中间体的相对能量和几何构型、与中间体相关的红外光谱和核磁共振谱以及过渡态能量，从而阐明催化反应中选择性的来源并指导未来的合成设计。该项目还将包括对可用于计算有机金属31P核磁共振化学位移和1JRh-P耦合的计算方法的评估。一旦确定了可靠的方法，31P核磁共振谱的计算机辅助分配可能会在机理研究中产生变革，允许常规表征和跟踪催化中间体。现场工作将利用UIUC核磁共振设施获取光谱。PI的电子结构计算结果将与实验相结合，通过对最近发现的催化过程的反应机理进行表征，并通过预测改性催化剂和底物的结果，实现合成方面的进步。结果将把化学反应的范围扩大到新的底物或产品，特别是用于药物开发和制造，并促进更绿色化学工艺的发展。

Non-technical DescriptionChemical reactions between metals and organic compounds may be complex and it is common for there to be numerous steps in a reaction process. A better understanding of the mechanisms and potential molecular structures involved in these reactions is needed both to optimize processes and to predict the molecular structures that can result from these industrially important reactions. The PI will conduct research at the University of Illinois Urbana-Champaign (UIUC), where she and her collaborators will focus on reactions such as those used for the synthesis of drug candidates and pharmaceuticals. The resources available at the National Center for Supercomputing Applications at UIUC will be used to conduct work grounded in the PI's computational chemistry background. The availabilities of the computing power and advanced instruments for chemical analysis at UIUC will be of great value in unraveling the reaction mechanisms under study. In addition to having access to these facilities, the PI and her students from Wichita State University will form a close collaboration with an active research group at UIUC, thereby strengthening the partnership between the institutions. Technical DescriptionThe fellowship will support the PI's activities at UIUC to computationally characterize regioselective additions to olefins, catalyzed by rhodium and iridium phosphine complexes. Synergistic computation-experiments will develop a framework to guide synthetic advances. Electronic structure calculations will be used to acquire relative energies and geometries of organometallic complexes, catalytic intermediates, IR and NMR spectra associated with intermediates, and transition state energies, to thereby elucidate the origins of selectivity in catalyzed reactions and guide the design of future syntheses. The project will also include an assessment of the computational methods available for calculation of organometallic 31P NMR chemical shifts and 1JRh-P coupling. Once reliable methods are identified, computationally-assisted assignment of 31P NMR spectra could be transformational in mechanistic studies, allowing for routine characterization and tracking of catalytic intermediates. On-site work will take advantage of the UIUC NMR facility to acquire spectra. The results of electronic structure calculations by the PI will be coupled with experiments to enable advancements in synthesis, through characterization of reaction mechanisms for recently discovered catalytic processes, and by predicting outcomes of modified catalysts and substrates. Results will expand the scope of chemical reactions to new substrates or products, particularly for drug development and manufacture, and facilitate development of greener chemical processes.