Studies in Physical Organic Chemistry

在有机动力学项目和数学与物理科学理事会多学科活动办公室的支持下，耶鲁大学化学系的Kenneth B. Wiberg教授研究了控制有机分子性质、反应和反应性的因素。通过实验和理论方法的结合，Wiberg教授解决了小环化合物中可能的结构扭曲程度，以及这种扭曲导致的能量和其他特性的变化。碳桥式螺戊烷预计具有非常高的环畸变度，理论表明在中心碳上存在近乎线性的键角。相关螺戊基阳离子的理论和结构研究解决了控制这些体系中观察到的两种不同类型重排的因素。小环炔的结构和稳定性以及亚甲基和高锰酸盐对碳-碳双键的攻击等问题也是合成和理论分析的目标。Wiberg教授还探讨了单取代环己烷中赤道构象偏好的大小和起源，重点是仔细分析甲基的构象偏好和熵项在确定构象偏好中的作用。有关有机分子的结构和反应性的理论继续得到实验的检验，通过制备旨在探索化学键的极限的分子，并在理论上通过计算分析这些分子中的键问题。耶鲁大学化学系的Kenneth B. Wiberg教授在有机动力学项目和数学与物理科学理事会多学科活动办公室的支持下，探索已知或预计会表现出极端结构扭曲的分子。这些研究的目标是一些类型的分子，特别是那些形成小环的碳原子的键角在没有这些小环强制的几何形状的情况下被迫明显偏离其首选值的分子。通过这些研究，威伯格教授获得了有关控制有机分子的性质、反应和反应性的因素的基本知识。

With the support of the Organic Dynamics Program and the Office of Multidisciplinary Activities of the Mathematical and Physical Sciences Directorate, Professor Kenneth B. Wiberg, of the Department of Chemistry at Yale University, studies the factors that control the properties, reactions, and reactivity of organic molecules. Through a combination of experimental and theoretical approaches, Professor Wiberg addresses the degree of structural distortion possible in small-ring compounds and the changes in energy and other properties that result from such distortion. Carbon-bridged spiropentanes are expected to have a remarkably high degree of ring distortion, with theory suggesting the presence of a nearly linear bond angle at the central carbon. Theoretical and structural studies of related spiropentyl cations address the factors controlling the two different types of rearrangements observed for these systems. Questions related to the structure and stability of small-ring cycloalkynes and the attack by methylene and by permanganate on carbon-carbon double bonds are also targeted for synthetic and theoretical analysis. Professor Wiberg also explores the magnitude and the origin of the equatorial conformational preference in monosubstituted cyclohexanes, focusing on careful analysis of the conformational preference of the methyl group and on the role of entropy terms in determining conformational preferences. Theories regarding the structure and reactivity of organic molecules continue to be tested experimentally, through the preparation of molecules designed to probe the limits of chemical bonding, and theoretically, through the calculational analysis of bonding issues in such molecules. Professor Kenneth B. Wiberg, of the Department of Chemistry at Yale University, with the support of the Organic Dynamics Program and the Office of Multidisciplinary Activities of the Mathematical and Physical Sciences Directorate, explores molecules known or expected to display extreme structural distortions. These studies target a number of classes of molecules, particularly those in which bond angles at carbon atoms forming part of a small ring are forced to deviate markedly from their preferred values in the absence of the geometry enforced by these small rings. Through these studies, Professor Wiberg gains fundamental knowledge regarding the factors that control the properties, reactions, and reactivity of organic molecules.