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

在化学系化学结构、动力学和机理B（CSDM-B）项目的支持下，波特兰州立大学的大卫斯图尔特教授和特蕾莎麦考密克教授正在研究高价有机卤素的化学结构、成键模型和化学反应性的交叉。合成分子通过新药、农业进步和尖端技术改善日常生活。有机卤素是一类化合物，其可以通过充当引入关键结构组分的催化剂或试剂来促进这些分子的合成。在某些情况下，有机卤素可能会取代合成中常用的昂贵和稀有金属。为了充分认识超价有机卤素在合成中的潜力，需要对基本成键事件有更深入的了解。这将通过在这项工作中应用的实验和理论相结合的方法来实现。下一代科学家的培训将发生在这个奖项，包括研究生和本科生的研究。波特兰州立大学被公认为“第一代前进”机构，这使得第一代大学生在研究经验的包容性。最后，在这个奖项期间，主要研究人员将增加访问实验室研究的盲人高中生通过一天在PSU营。非共价键相互作用是超价有机卤素的反应性的基石，但基本的原子级属性，决定他们的力量还没有得到很好的理解。凭借该奖项，主要研究人员从多个角度解决了高价卤素的非共价相互作用。理论和经验的方法，以获得新的洞察卤素键合和二芳基碘鎓盐的双功能特性。他们将使用物理有机化学技术（电导，NMR滴定，动力学）和理论（DFT和NBO）的组合，将键合模型与结构和热力学/动力学反应性相关联。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）参与非共价相互作用时二芳基卤盐的双功能特性，以及3）基于双功能活化的二芳基卤盐与亲核试剂的反应。这些活动完成后，将有助于新的合成方法和有机合成催化剂的进步。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

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.