Matrix Isolation NMR Studies of Reactive Intermediates

Zilm教授得到了实验物理化学计划的资助，该计划利用核磁共振技术研究在低温基质中捕获的亚稳态分子碎片的结构，以便在固态中进行高分辨率研究。这些研究应该提供有关化学反应过程中形成的中间体的性质的信息，从而进一步了解化学反应是如何发生的。Zilm已经证明，固体核磁共振高分辨率技术提供的结构特定信息与反应中间体的基质分离技术相结合，是研究化学反应中产生的瞬时物种的有用工具。利用他开发的新的核磁共振技术，他将研究单重态双自由基、单重态卡宾和硅烯、单重态硝烯、芳醇和其他物种的结构。偶极耦合以及核间距离和键的相对取向将提供详细的结构，而化学位移张量将提供有关这些碎片中电子分布的额外信息。在20K下工作将提高核磁共振技术的灵敏度。

Professor Zilm is supported by a grant from the Experimental Physical Chemistry Program to study the structure of metastable molecular fragments captured in a low temperature matrix using nuclear magnetic resonance (NMR) techniques for high resolution studies in the solid state. These studies should provide information on the nature of the intermediates formed during the course of a chemical reaction and thus further our understanding of how chemical reactions occur. A combination of the structure-specific information from high-resolution techniques of solid state NMR and the matrix isolation techniques for reactive intermediates have been demonstrated by Zilm as a useful tool for the transient species produced in a chemical reaction. With new NMR techniques that he has developed he will investigate the structure of singlet biradicals, singlet carbenes and silylenes, singlet nitrenes, ynols, and other species. Dipolar couplings and therefore internuclear distances and relative orientations of bonds will provide detailed structure, and chemical shift tensors will provide additional information about the electron distribution in these fragments. Sensitivity of the NMR techniques will be increased by operating at 20 K.