Bicyclic-Constrained Alkyl Groups for Control of Reactivity

有机动力学项目的这项资助支持了斯蒂芬·F·尼尔森在威斯康星州/麦迪逊大学。 将研究由四取代的C=C、C=N、N=N、含氧的N=N和三取代的N=S官能团的氧化产生的自由基阳离子和双阳离子。通过从双键连续去除一个和两个电子，将产生具有一个正电荷单元（自由基阳离子）和两个正电荷单元（双阳离子）的物质。 这些反应性中间体作为几何形状的函数的稳定性将通过将它们并入双环中来追求。环尺寸的变化将允许作为环尺寸的函数的反应性的调查和穿过中等大小的环的空间相互作用。各种光谱和电化学技术将被用来表征自由基阳离子和dications。ESR将是用于阐明结构细节的主要光谱工具。 在氧化条件下形成的活性中间体的产生、稳定和表征将推进对有机氧化反应的基本理解，并确定分子结构在促进或抑制氧化中的重要作用。

This grant in the Organic Dynamics Program supports the research of Professor Stephen F. Nelsen at the University of Wisconsin/Madison. Radical cations and dications generated by oxidation of tetrasubstituted C=C, C=N, N=N, oxygenated N=N, and trisubstituted N=S functionalities will be studied. By successive removal of one and two electrons from the double bonds, species with one unit of positive charge (radical cations) and two units of positive charge (dications) will be generated. The stability of these reactive intermediates as a function of geometry will be pursued by incorporating them into bicyclic rings. Variation of the ring size will permit an investigation of reactivity as a function of ring size and through-space interactions across medium sized rings. A variety of spectroscopic and electrochemical techniques will be used to characterize radical cations and dications. ESR will be the prime spectroscopic tool that will be used to elucidate structural details. The generation, stabilization, and characterization of reactive intermediates formed under oxidative conditions will advance the fundamental understanding of organic oxidation reactions and define the important role of molecular structure in facilitating or inhibiting oxidations.