Absolute Kinetic Studies of Carbene Fragmentation and Related Reactions

有机化学和高分子化学项目继续支持新泽西州罗格斯大学新不伦瑞克校区化学系罗伯特·A·莫斯博士的工作。这项研究包括对激光闪光光解产生的卡宾和相关活性中间体的基础研究，以及随后的紫外光和红外吸收。特别令人感兴趣的是烷氧基卤代卡宾(ROCX)的裂解反应的研究，其中速率和路径预计取决于R基团和卤素X的性质。分子内重排中的量子力学隧道将使用环丙基甲基卡宾C3H5CH2CCl和C3H5CD2CCl进行研究。与理论家合作进行的高水平计算研究将伴随着实验工作进行。这项正在进行的研究涉及卡宾的基础研究-卡宾是短暂的、活性的中间体，只有两个基团连接到碳上，而不是通常的四个基团-可以通过非常短的激光闪光在溶液中产生。然后，中间体的浓度可以通过它们对紫外光或红外光的吸收来跟踪。这是经典的物理有机化学，通过使用严格的科学方法和涉及的各种策略和技术，预计将为参与的学生和同事提供出色的培训。

With this renewal award the Organic and Macromolecular Chemistry Program continues its support for the work of Dr. Robert A. Moss of the Department of Chemistry at Rutgers University New Brunswick campus in New Jersey. The research involves fundamental studies of carbenes and related reactive intermediates generated by laser flash photolysis, and followed by UV and IR absorption. Of particular interest is the study of the fragmentation reactions of alkoxyhalocarbenes (ROCX), where the rates and pathways are expected to depend on the natures of the R group and the halogen X. Quantum mechanical tunneling in intramolecular rearrangements will be studied using the cyclopropylmethyl carbenes C3H5CH2CCl and C3H5CD2CCl. High level computational studies carried out in collaboration with theoreticians will accompany the experimental work.This ongoing research involves fundamental studies of carbenes - short-lived and reactive intermediates with only two groups attached to carbon rather than the usual four - which can be generated in solution by very short laser flashes. The concentrations of the intermediates can then be followed by their absorption of ultraviolet or infrared light. This is classical physical organic chemistry, and is expected to provide excellent training for the students and colleagues involved, through the rigorous scientific approach used and the variety of strategies and techniques involved.