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

含缺电子主族原子的高反应性物质的动力学和机理研究以及新型分子的合成

• 批准号: 9981759
• 负责人: Peter Gaspar
• 金额: $ 50.48万
• 依托单位: Washington University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-01-01 至 2003-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9981759&HistoricalAwards=false
• 关键词: Kinetic; Mechanistic; Studies; Highly; Reactive

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.

有机化学和高分子化学项目继续支持圣路易斯华盛顿大学化学系彼得·P·加斯帕博士的工作。这项工作的目的是了解控制电子缺乏和多键有机分子反应的因素，除了更常见的元素C，N和O之外，还包括Si，P，S和Sn元素。人们相信，通过制造这些新的分子，并研究它们的反应机理，将有可能将有机化学的强大机制思想扩展到整个元素周期表中的成键和断键过程的预测。一种强大的新仪器已经开发出来，它将简化新的活性物种的鉴定，这可能导致具有特殊和有用性质的新材料。一些被研究的分子包括(IPr3Si)2Si，它类似于卡宾，可能有一个单态或三重态的电子基态，PCSiMe3，在P和C之间有一个三键，类似于有机腈，以及BN，一种不稳定的分子，已经用光谱检测到了，但其化学组成尚不清楚。BN将在新的超音速流动热解喷嘴装置中产生，并在电荷交换或其他离子-分子反应后用FT离子回旋共振质谱仪进行检测。