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: 0316124
• 负责人: Peter Gaspar
• 金额: --
• 依托单位: Washington University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2003
• 资助国家: 美国
• 起止时间: 2003-07-15 至 2009-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0316124&HistoricalAwards=false
• 关键词: Kinetic; Mechanistic; Studies; Highly; Reactive

The goal of this project is to understand the factors that control the reactions of electron-deficient and multiply bonded species containing second-, third- and fourth-row elements of groups 13, 14, and 15. The generation of dimethyldisilyne (MeSiSiMe) will be explored in order to address the structure and reactivity of molecules containing the silicon-silicon triple bond, as yet unknown. A novel class of electron-deficient species containing four valence electrons at the reactive atom, both charged (e.g. Br-C:+ and Ph-Si:+) and neutral (Ph-B: and Ph-Al:), offer the capability of forming three new bonds in either a concerted or stepwise manner. New precursors for reactive stannylenes (R2Sn:) will allow the exploration of the full range of reactions available to neutral molecules containing divalent tin atoms, without the presence of sterically shielding substituents. Sterically unencumbered lithiosilylenes R(Li)Si: will be used for the exploration of the chemistry of triplet silylenes, and a new program will be initiated for the design and construction of "molecular vices" that are rigid scaffolds capable of imposing preselected large bond angles on divalent species mounted between the jaws. This will allow the study of the spectroscopy and chemistry of molecules in unusual electronic states like triplet silylenes.The study of reactive carbon-based intermediates has shed light on the fundamental mechanisms by which organic reactions occur, providing both basic understanding and predictive tools for the control of organic reactivity. With the support of the Organic and Macromolecular Chemistry Program, Professor Peter P. Gaspar, of the Department of Chemistry at Washington University, is studying the preparation and reactivity of analogous species based on the heavier elements in the carbon group - silicon, germanium, and tin. These studies will lead to the extension of the powerful mechanistic ideas of organic chemistry to the prediction and rationalization of bond-making and bond-breaking processes throughout the periodic table, and in addition will provide predictive insights into the factors controlling the reactions involved in the chemical vapor deposition of silicon films that form the basis of much of the modern semiconductor industry.

该项目的目的是了解控制电子缺陷和多键键的反应的因素，这些物种包含第13、14和15组的第二，第三和第四行元素。将探索Dimethyldisilyne的产生（分子），以解决将Silicon-Silicon-silic-silic-silic-silic-silic-silic-nononing Nononing既定的分子的结构和反应性探索。一类新型的电子缺陷物种，该物种在反应性原子上包含四个价电子，均为充电（例如BR-C：+和PH-SI：+）和中性（pH-B：和pH-al :)，具有以协调或逐步的方式形成三个新键的能力。反应性stannylenes（R2SN :)的新前体将允许探索含有二价锡原子的中性分子可用的各种反应，而不会存在空间屏蔽的取代基。在空间上不受限制的石硅烷基烯丙基r（li）si：将用于探索三胞胎二莲烯烯丙基苯乙烯化学的化学，并将启动一个新程序，用于设计和构建“分子恶化”，这些“分子恶化”是刚性支架，能够在Jaws之间扎根于划分的划分的大键角。这将允许研究不寻常的电子状态（如三角甲硅烷基）的分子的光谱和化学。对反应性碳基中间体的研究揭示了发生有机反应的基本机制，从而为有机反应的控制提供了基本的理解和预测性工具。在有机和大​​分子化学计划的支持下，华盛顿大学化学系的彼得·P·加斯帕（Peter P. Gaspar）教授正在研究基于碳群中较重的元素 - 硅，锗和锡的较重元素的类似物种的制备和反应性。这些研究将导致有机化学的强大机械思想扩展到整个周期表中建立键和断开键合过程的预测和合理化，此外，还将为控制硅膜化学蒸气沉积中涉及的反应的因素提供预测的见解，这些因素构成了现代半导体工业的基础。