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

RII 轨道 4：电子结构计算，用于表征烯烃区域选择性加成的机制，并推进 P-31 NMR 作为催化中间体的报告基因

• 批准号: 1738708
• 负责人: Katie Mitchell-Koch
• 金额: $ 17.63万
• 依托单位: Wichita State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-09-15 至 2022-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1738708&HistoricalAwards=false
• 关键词: RII; Track; Electronic; Structure; Calculations

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.

金属和有机化合物之间的化学反应可能很复杂，在一个反应过程中通常有许多步骤。需要更好地了解这些反应的机制和潜在的分子结构，以优化工艺并预测这些工业上重要的反应可能产生的分子结构。PI将在伊利诺伊大学厄巴纳-香槟分校（UIUC）进行研究，在那里她和她的合作者将专注于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揭示所研究的反应机制具有重要价值。除了可以使用这些设施外，威奇托州立大学的PI和她的学生将与UIUC的一个活跃的研究小组密切合作，从而加强机构之间的伙伴关系。技术描述该奖学金将支持PI在UIUC的活动，以计算表征由铑和铱膦配合物催化的烯烃的区域选择性添加。协同计算实验将形成一个指导合成进步的框架。电子结构计算将用于获得有机金属配合物的相对能量和几何形状、催化中间体、与中间体相关的IR和NMR光谱以及过渡态能量，从而阐明催化反应选择性的起源，并指导未来合成的设计。该项目还将包括评估用于计算有机金属31P核磁共振化学位移和1JRh-P耦合的计算方法。一旦确定了可靠的方法，31P核磁共振谱的计算辅助分配可能在机理研究中发生转变，允许常规表征和催化中间体的跟踪。现场工作将利用UIUC核磁共振设备获取光谱。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，并预测改性催化剂和底物的结果，从而实现合成的进步。结果将扩大化学反应的范围到新的底物或产品，特别是药物开发和制造，并促进绿色化学过程的发展。