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: 9108130
• 负责人: Peter Gaspar
• 金额: $ 72.83万
• 依托单位: Washington University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1991
• 资助国家: 美国
• 起止时间: 1991-06-01 至 1996-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9108130&HistoricalAwards=false
• 关键词: Kinetic; Mechanistic; Studies; Highly; Reactive

Various highly reactive intermediates will be generated and a study will be made of their reaction mechanisms. These highly reactive intermediates will be generated by photolysis and by pyrolysis of appropriate precursors. Decay kinetics of these species will be followed by time-resolved spectroscopy following laser flash photolysis. Chemical reactivity of these intermediates will be probed through trapping experiments and product studies. The molecules to be studied include species containing divalent silicon, germanium, and tin atoms, namely, silylenes, germylenes, and stannylenes, respectively. Reaction pathways for the monovalent six-valence-electron species nitrenes (R-N:) and phosphinidenes (R-P:), and of the monovalent four-valence-electron borylenes (R-B:) and aluminylidenes (R-Al:) will be compared with reaction paths for the corresponding carbenes, silylenes, and germylenes. Molecules will be synthesized with new kinds of bonds, including silicon-silicon and silicon-germanium triple bonds, and silicon-transition metal double bonds. New ring systems will be prepared as well. %%% This grant from the Organic Dynamics Program supports the continuing work of Professor Peter P. Gaspar at Washington University. Reactive intermediates will be generated that contain silicon, germanium, tin, phosphorous, aluminum, and boron atoms that have less than their normal complement of bonds. These reactive intermediates will be generated from stable precursor molecules by photolysis and by thermolysis methods. The steps by which these intermediates decompose will be studied as well as the rate at which these processes occur. More direct evidence for these reactive intermediates will be given by trapping them with other molecules. The products of these trapping experiments will reveal the structure of the intermediates. Compounds with silicon- silicon single and double bonds are known. Now even more reactive molecules will be synthesized with silicon-silicon and silicon- germanium triple bonds. New ring systems will also be prepared.

将产生各种高反应性中间体，并将对其反应机制进行研究。这些高反应性的中间体将通过光解和适当的前体的热解产生。这些物种的衰减动力学将在激光闪光光解过程后进行时间分辨光谱。这些中间体的化学反应性将通过捕获实验和产品研究来探测。 要研究的分子包括含有二价硅，锗和锡原子的物种，即分别是甲硅烷基烯，生殖器和stannylenes。单价六价电子物种硝酸（R-n：：：：：cyply）和磷酸烯（R-P：：：：：：：：：：：：分子将与新型键合成，包括硅 - 硅和硅三键以及硅 - 转变金属双键。新的环系统也将准备。 %% %%来自有机动力学计划的这笔赠款支持华盛顿大学的彼得·P·加斯帕教授的持续工作。将产生包含硅，锗，锡，磷，铝和硼原子的反应性中间体，这些原子的键含量小于正常的键补体。这些反应性中间体将通过光解和热解方法从稳定的前体分子产生。将研究这些中间体分解的步骤以及这些过程的发生率。这些反应性中间体的更直接证据将通过与其他分子一起捕获。这些捕获实验的产物将揭示中间体的结构。具有硅单键和双键的化合物已知。现在，将与硅 - 硅和硅晶三键合成更具反应性的分子。新的环系统也将准备。