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.

将产生各种高活性中间体， 并对其反应机理进行了研究。这些高度 反应性中间体将通过光解和 适当的前体的热解。这些的衰变动力学 物种将遵循时间分辨光谱， 激光闪光光解这些中间体的化学反应性 将通过捕集实验和产物研究进行探索。 待研究的分子包括含有二价 硅、锗和锡原子，即亚甲硅烷基，亚甲锗烷基， 和亚锡烷基。反应途径 单价六价电子物种氮烯（R-N：）和 膦烯（R-P：），具有一价四价电子 亚硼基（R-B：）和亚铝基（R-Al：）将与 相应的碳烯、亚甲硅烷基和 锗烯。分子将被合成为新的键， 包括硅-硅和硅-锗三键，以及 硅-过渡金属双键。新的环系统将 也准备好了。 %%% 有机动力学计划的这笔赠款支持 彼得·P·加斯帕教授在华盛顿的继续工作 大学将产生反应性中间体，其含有 硅、锗、锡、磷、铝和硼原子 它们的键数少于正常的键数。这些 反应性中间体将从稳定的前体产生 分子通过光解和热分解的方法。采取步骤 这些中间体的分解也将被研究， 这些过程发生的速率。更直接的证据表明， 这些反应性中间体将通过用以下物质捕获它们而得到： 其他分子。这些诱捕实验的产物 揭示了中间体的结构。含硅化合物- 硅单键和双键是已知的。现在反应更激烈了 分子将由硅-硅和硅- 锗三键还将准备新的环形系统。