RUI: Reactive Intermediates and Unusual Molecules from Phenanthrene-based Precursors

在化学系化学结构、动力学和机理B(CSDM-B)计划和既定的激发竞争研究计划(EPSCoR)的支持下，科尔比学院化学系的Dasan Thamattoor教授和他的本科生团队正在进行一项关于菲前体产生的活性中间体和特殊分子的研究。具有学术和实际意义的目标化学物种的结构和反应性将通过实验和现代计算方法进行研究。此外，还将开展几项举措，为本科生创造有意义的研究经验，促进有学生参与的国际研究合作，并促进地区学校K-12学生的高质量科学教育。单一乙烯基卡宾在环丙烯异构化和其他重要的合成转化中发挥关键作用。然而，人们对它们的化学成分知之甚少。同样，关于环丙叉(最小的碳环卡宾)及其衍生物的动力学和结构的实验数据也相当稀少。在这项建议中，将使用环丙烷化的菲前体来研究乙烯基卡宾和环丙叉的结构和反应活性。此外，还将寻求使用环丁化菲作为烯烃和烯的来源的创新方法。这些研究将使用一系列的实验方法，如稳态光解、EPR光谱、基质隔离光谱和时间分辨激光闪光光解以及现代计算工具。建议的前体的现成合成、稳定性、易操作性和多功能性使这些项目成为涉及本科生的理想项目。这项拟议的工作融合了合成、机械和计算有机化学，旨在为学生提供全面的研究体验，激发他们的好奇心，并让他们作为合作伙伴参与发现过程。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With support from the Chemical Structure, Dynamics & Mechanism-B (CSDM-B) Program of the Chemistry Division and the Established Program to Stimulate Competitive Research (EPSCoR), Professor Dasan Thamattoor of the Department of Chemistry at Colby College and his team of undergraduate students are undertaking a study of reactive intermediates and unusual molecules generated from phenanthrene-based precursors. The structure and reactivity of the targeted chemical species, which are of academic as well as practical interest, will be investigated experimentally and by modern computational methods. In addition, several initiatives to create meaningful research experiences for undergraduates, foster international research collaborations with student participation, and promote high-quality science education for K-12 students in area schools will be pursued.Singlet vinylcarbenes play a key role in cyclopropene isomerizations and other important synthetic transformations. Yet little is known about their chemistry. Likewise, experimental data on the kinetics and structure of cyclopropylidene, the smallest carbocyclic carbene, and its derivatives, are quite sparse. In this proposal, cyclopropanated phenanthrene precursors will be used to investigate the structure and reactivities of vinylcarbenes and cyclopropylidenes. Furthermore, innovative approaches to using cyclobutanated phenanthrenes as sources of ketenes and allenes will be pursued. A broad range of experimental methods such as steady state photolysis, EPR spectroscopy, matrix isolation spectroscopy, and time-resolved laser flash photolysis as well as modern computational tools will be used in these investigations. The ready synthesis, stability, ease of handling, and versatility of the proposed precursors make these projects ideal for involving undergraduate students. The proposed work, which integrates synthetic, mechanistic, and computational organic chemistry, is designed to provide students with a comprehensive research experience, pique their curiosity, and engage them as partners in the discovery process.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.