CAS: Interrogating the Intersection of Structure, Bonding, and Reactivity of Hypervalent Halogens

CAS：探究高价卤素的结构、键合和反应性的交叉点

• 批准号: 2154500
• 负责人: David Stuart
• 金额: $ 44.28万
• 依托单位: Portland State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-09-01 至 2025-08-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154500&HistoricalAwards=false
• 关键词: CAS; Interrogating; Intersection; Structure; Bonding

With the support of the Chemical Structure, Dynamics, and Mechanisms B (CSDM-B) Program in the Division of Chemistry, Professors David Stuart and Theresa McCormick of Portland State University are studying the intersection of chemical structure, bonding models and chemical reactivity of hypervalent organohalogens. Synthetic molecules enhance daily life through new medicine, agricultural advances, and cutting-edge technologies. Organohalogens are a class of compound that may facilitate the synthesis of these molecules by acting as catalysts or reagents that introduce key structural components. In some cases, it is probable that organohalogens may replace expensive and rare metals that are commonly used in synthesis. To fully realize the potential of hypervalent organohalogens in synthesis, a deeper understanding of fundamental bonding events is needed. This will be achieved through a combined experimental and theoretical approach applied in this work. Training of the next generation of scientists will occur with this award by including graduate and undergraduate students in research. Portland State University is recognized as a “First-gen Forward” Institution, which enables inclusion of first-generation college students in research experiences. Finally, during this award period the principal investigators will increase access to laboratory research for blind high school students through a day camp at PSU.Non-covalent bonding interactions are a cornerstone of the reactivity of hypervalent organohalogens, yet the underlying atomic-level properties that dictate their strength are not well understood. With this award, the principal investigators tackle non-covalent interactions of hypervalent halogens from multiple perspectives. Both theoretical and empirical approaches are employed to gain new insight into halogen bonding and the bifunctional character of diaryliodonium salts. They will use a combination of physical organic chemistry techniques (conductance, NMR titration, kinetics) and theory (DFT and NBO) to correlate bonding models with structure and thermodynamic/kinetic reactivity. They will specifically focus on three key areas: 1) the orbital interaction of halogen atoms in halogen-bond donors, 2) bifunctional character of diarylhalonium salts when participating in non-covalent interactions, and 3) reactions of diarylhaloniums with pronucleophiles based on bifunctional activation. These activities, when completed, would contribute to advances in new synthetic methods and catalysis for organic synthesis.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学结构，动力学和机制B（CSDM-B）计划的支持下，波特兰州立大学的David Stuart和Theresa McCormick教授正在研究化学结构，键合模型和高价值有机热的化学反应性的交集。合成分子通过新医学，农业进步和尖端技术来增强日常生活。有机热量是一类化合物，可以通过充当引入关键结构成分的催化剂或试剂来支持这些分子的合成。在某些情况下，有问题的是，有机热量可能取代了合成中通常使用的昂贵且稀有的金属。为了充分意识到合成中高价值的有机脂蛋白的潜力，需要对基本键合事件有更深入的了解。这将通过在这项工作中采用的合并实验和理论方法来实现。通过包括研究生和本科生在研究中，将对下一代科学家进行培训。波特兰州立大学被公认为是“第一代远期”机构，该机构使第一代大学生包括研究经验。最后，在此奖项期间，首席研究人员将通过PSU的一日营增加对盲人高中学生的实验室研究的访问权限。没有可可的粘结相互作用是高价值有机凝胶反应性的基石，但基本的原子级特性却不理解其强度的理解。通过该奖项，主要研究人员从多个角度解决了高价值卤素的非共价互动。理论方法和经验方法均采用了对卤素键合的新见解和日二元盐盐的双功能特征。他们将结合物理有机化学技术（电导，NMR滴定，动力学）和理论（DFT和NBO）将键合模型与结构和热力学/动力学反应相关联。他们将特别关注三个关键领域：1）卤素键供体中卤素原子的轨道相互作用，2）日二维体盐的双功能特征当参与非共价相互作用时，以及3）二二元基于双功能活化的二芳香族的反应。这些活动完成后，将有助于新的合成方法的进步和有机合成的催化。该奖项反映了NSF的法定任务，并使用基金会的知识分子优点和更广泛的影响评估标准，通过评估被认为是宝贵的支持。