Kinetic and Mechanistic Studies of Highly Reactive Species Containing Electron-Deficient Main Group Atoms, and the Synthesis of Novel Molecules

随着这一奖项的更新，有机和大分子化学项目继续支持圣路易斯华盛顿大学化学系Peter P. Gaspar博士的工作。这项工作的目标是了解控制电子缺陷和多键有机分子的反应的因素，这些有机分子除了含有更常见的元素如C， N和o外，还含有Si， P， S和Sn。相信通过制造这些新分子，并研究它们的反应机制，这将有可能把有机化学的强大的机械思想扩展到整个元素周期表中键的形成和断裂过程的预测。一种功能强大的新装置已经开发出来，它将简化新反应物质的鉴定，从而可能产生具有不同寻常和有用性能的新材料。一些被研究的分子是（iPr3Si）2Si，它类似于碳，可能具有单线态或三重态电子基态；PCSiMe3，在P和C之间有三键，类似于有机腈；BN，一种不稳定的分子，已被光谱检测到，但其化学性质未知。在新型的超音速流动热解喷嘴装置中生成BN，通过电荷交换或其他离子-分子反应，用FT离子回旋共振质谱法检测BN。

With this renewal award the Organic and Macromolecular Chemistry Program continues its support for the work of Dr. Peter P. Gaspar in the Department of Chemistry at Washington University in St louis. The goal of the work is to understand the factors that control the reactions of electron deficient and multiply bonded organic molecules containing the elements Si, P, S and Sn, in addition to the more common elements like C, N, and O. It is believed that by making these novel molecules, and studying the mechanisms of their reactions, it will be possible to extend the powerful mechanistic ideas of organic chemistry to the prediction of bond-making and -breaking processes throughout the periodic table. A powerful new apparatus has been developed which will simplify the identification of new reactive species which may lead to new materials with unusual and useful properties.Some of the molecules to be investigated are (iPr3Si)2Si, which is analogous to a carbene and may have either a singlet or a triplet electronic ground state, PCSiMe3, with a triple bond between the P and the C, analogous to an organic nitrile, and BN, an unstable molecule which has been detected spectroscopically but whose chemistry is unknown. BN will be generated in the new supersonic flow pyrolysis nozzle apparatus, and detected by FT ion cyclotron resonance mass spectroscopy after charge exchange or other ion-molecule reactions.