Absolute Kinetic Studies of Intramolecular and Intermolecular Carbenic Reactions

这项来自有机动力学项目的资助支持了罗格斯大学Robert A. Moss教授的持续工作。卡宾和相关的反应中间体将通过直接光谱方法，特别是激光闪光光解进行研究。项目内容包括：(1)剖析光引发的碳化合物反应，揭示受激发态前体（模拟碳化合物反应）污染的情况；(2)同位素对分子内重排的影响，以及隧道效应的证据；(3)不对称环取代环丙基卤代烃竞争性1,2-碳迁移的电子和空间效应研究；(4)测定了酰基氧基羰基中1,2-酰基迁移的电子特性，以及酰基氧基二氮基的碱性裂解可能产生酰基阴离子；(5)测定了碳-吡啶酰化物的生成动力学。碳烯是一种二价碳，是有机化学中重要的反应中间体。本课程将研究碳化合物的反应，如氢和碳原子的迁移模式，以及碳化合物前体光解产物的来源。这项研究可能会为我们对碳化学的理解带来新的见解。

This grant from the Organic Dynamics Program supports the continuing work of Professor Robert A. Moss at Rutgers University. Carbenes and related reactive intermediates will be studied by direct spectroscopic methods, particularly by laser flash photolysis. Elements of the project are: (1) dissection of the photoinitiated carbenic reactions to reveal contamination by excited state precursors (carbene mimetic reactions); (2) examination of isotope effects on intramolecular rearrangements, and evidence for tunneling; (3) the study of electronic and steric effects in competitive 1,2-carbon migrations of unsymmetrically ring-substituted cyclopropylhalocarbenes; (4) the measurement of the electronic character of 1,2-acyl migrations in acyloxycarbenes and the possible generation of acyl anions by the basic cleavage of acyloxydiazirenes; and (5) determination of the kinetics of carbene-pyridine ylide formation. Carbenes, divalent carbon species, are important reactive intermediates in organic chemistry. Aspects of the reactions of carbenes will be studied such as the mode of hydrogen and carbon atom migrations and the origin of the products of photolysis of carbene precursors. This research could lead to new insights in our understanding of carbene chemistry.