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

这项来自有机动力学项目的拨款支持杜克大学爱德华·m·阿内特教授的持续工作。用量热法和电化学技术测定各种有机化合物的异解热、均解热和电子转移热。杂解键强度将由碳亲电试剂（例如，碳离子、羰基功能、迈克尔受体、活化芳烃）与广泛的亲核试剂（例如，碳离子、酰化物、烷氧化物、硫酸盐、硝基阴离子）的反应热来确定。这些实验将用于直接比较共价键的异裂和均裂。这项工作将允许建立一个基本的热力学框架，通过这个框架，可以直接比较许多与碳成键和断键的过程。将为碳原子和杂原子之间的键建立一个热力学框架。量热法和电化学技术是实验方法的选择。通过测量键的离解能和离子种之间的反应热，可以确定大谱键的共同尺度。从这项研究中获得的数据将形成一个重要的热力学数据库，为所有有机反应的成键/断键过程提供基本的见解。

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.