Carbon Affinities-Energetics of Bond Formation and Cleavage of Organic Compounds

碳亲和力-有机化合物键形成和断裂的能量

• 批准号: 9218375
• 负责人: Edward Arnett
• 金额: $ 34.98万
• 依托单位: Duke University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1992
• 资助国家: 美国
• 起止时间: 1992-12-15 至 1996-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9218375&HistoricalAwards=false
• 关键词: Carbon; Affinities; Energetics; Bond; Formation

This grant from the Organic Dynamics Program supports the continuing work of Professor Edward M. Arnett at Duke University. Heats of heterolysis, homolysis and electron transfer for a wide spectrum of organic compounds will be determined using calorimetry and electrochemical techniques. The heterolytic bond strengths will be determined from heats of reactions of carbon electrophiles (e.g., carbenium ions, carbonyl functions, Michael acceptors, activated aromatics) with a wide range of nucleophiles (e.g., carbanions, ylides, alkoxides, thiolates, nitroanions). These experiments will be used to compare directly heterolytic and homolytic cleavages of covalent bonds. This work will allow the building of a basic thermodynamic framework by which many processes for making and breaking bonds to carbon can be compared directly. %%% A thermodynamic framework will be built for bonds between carbon and hetero atoms. Calorimetry and electrochemical techniques are the experimental methods of choice. By measuring bond dissociation energies and the heats of reaction between ionic species, a common scale can be determined for a large spectrum of bonds. The data to be obtained from this research will form an important thermodynamic database that is to provide fundamental insight in the bond making/breaking processes of all organic reactions.

有机动力学计划的这笔赠款支持 爱德华·M教授的工作。阿内特在杜克大学 大学 异裂热、均裂热和电子热 广泛的有机化合物的转移将是 使用量热法和电化学技术测定。 异裂结合强度将由以下热测定： 碳亲电试剂的反应（例如，碳正离子， 羰基官能团、迈克尔受体、活化芳族化合物） 具有宽范围的亲核试剂（例如，碳负离子，叶立德， 醇盐、硫醇盐、硝基阴离子）。 这些实验将 用于直接比较异裂和均裂的裂解， 共价键 这项工作将允许建立一个基本的 热力学框架，许多制造和 可以直接比较碳的断裂键。 %%% 将建立一个热力学框架， 碳和杂原子。量热法和电化学 技术是实验方法的选择。 通过 测量键离解能和反应热 在离子种类之间，可以确定一个共同的尺度， 大范围的债券。 由此获得的数据 研究将形成重要的热力学数据库， 提供关于键形成/断开的基本见解， 所有有机反应的过程。