Absolute Kinetic Studies of Carbene Fragmentation and Related Reactions

卡宾裂解及相关反应的绝对动力学研究

• 批准号: 0091368
• 负责人: Robert Moss
• 金额: $ 44.5万
• 依托单位: Rutgers University New Brunswick
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-01-01 至 2004-10-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0091368&HistoricalAwards=false
• 关键词: Absolute; Kinetic; Studies; Carbene; Fragmentation

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.

有了这个更新奖的有机和高分子化学计划继续支持博士的工作。位于新泽西的罗格斯大学新玩法校区化学系的莫斯说。 本研究涉及激光闪光光解产生的卡宾及相关反应中间体的基础研究，以及随后的紫外和红外吸收。 特别感兴趣的是烷氧基卤代卡宾（ROCX）的断裂反应的研究，其中的速率和途径预计取决于R基团和卤素X的性质。 用环丙基甲基卡宾C3H5CH2CCl和C3H5CD2CCl研究分子内重排的量子力学隧穿。 在实验工作的同时，还将与理论工作者合作开展高水平的计算研究。这项正在进行的研究涉及卡宾的基础研究。卡宾是一种寿命短的活性中间体，只有两个基团连接在碳原子上，而不是通常的四个基团。 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，预计将通过使用严格的科学方法和所涉及的各种策略和技术，为相关的学生和同事提供出色的培训。