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

非技术性描述金属和有机化合物之间的化学反应可能很复杂，通常在反应过程中有许多步骤。需要更好地理解这些反应中涉及的机制和潜在的分子结构，以优化工艺并预测这些工业重要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，在那里她和她的合作者将专注于诸如用于候选药物和药物合成的反应。 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在揭示所研究的反应机理方面具有重要价值。除了有机会获得这些设施，PI和她的学生从威奇托州立大学将形成一个密切的合作与一个活跃的研究小组在UIUC，从而加强机构之间的伙伴关系。 技术说明该奖学金将支持PI在UIUC的活动，以计算表征铑和铱膦络合物催化的烯烃的区域选择性加成。协同计算实验将开发一个框架，以指导合成的进步。电子结构计算将被用来获得相对能量和几何的有机金属配合物，催化中间体，IR和NMR光谱与中间体，过渡态能量，从而阐明在催化反应的选择性的起源，并指导未来的合成设计。 该项目还将包括评估可用于计算有机金属31 P NMR化学位移和1 JRh-P耦合的计算方法。一旦确定了可靠的方法，31 P NMR光谱的计算辅助分配可能在机理研究中具有变革性，从而可以对催化中间体进行常规表征和跟踪。现场工作将利用UIUC NMR设施获取光谱。PI的电子结构计算结果将与实验相结合，通过表征最近发现的催化过程的反应机制，以及预测改性催化剂和底物的结果，从而促进合成。研究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，并促进更绿色的化学过程的开发。

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.