Group 14 Reactive Intermediates & Organic/Organometallic Photochemistry

第 14 组 反应中间体

• 批准号: 38211-2012
• 负责人: Leigh, William
• 金额: $ 5.1万
• 依托单位: McMaster University
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2012
• 资助国家: 加拿大
• 起止时间: 2012-01-01 至 2013-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=513439
• 关键词: Group; 14; Reactive; Intermediates; Organic

Our NSERC Discovery program focuses on fast kinetics studies of the reactions of divalent and multiply-bonded molecules containing one or more of the heavy tetrel elements (Si, Ge, and Sn), with a view to the development of a comprehensive understanding of their reaction mechanisms and the way they vary with the central element and the electronic and steric characteristics of substituents. Most of the molecules we study are highly reactive, transient species, which we generate using pulsed laser-induced photochemical reactions and detect and monitor directly using fast time-resolved uv-vis spectroscopy. Part of our work involves studying stable molecules containing these functionalities, which can be prepared in advance; their (typically fast) reactions are studied by stopped-flow kinetics, another fast time-resolved spectroscopic method. Our work bridges between the mechanistic behaviour of simply substituted divalent and multiply-bonded derivatives that theory can address with high precision, and the sterically-hindered ones that are of primary interest to synthetic chemists. Molecules of these types hold great potential for applications in synthesis and materials chemistry, and are also relevant to the chemistry of silicon & germanium semiconductor surfaces, for which appropriately substituted derivatives serve as small molecule models. Developing a detailed understanding of the chemistry of these species in various structural situations and under various experimental conditions, and of the mechanisms and scope of the photochemical reactions which produce them, is important for the development of new strategies in synthetic and materials chemistry which are based on the chemistry of these species. Our work serves as a fertile training ground for students in the chemical sciences, who represent the next generation of highly qualified Canadian scientists.

我们的NSERC发现计划专注于包含一个或多个重四元元素（Si，Ge和Sn）的二价和多键分子反应的快速动力学研究，以期全面了解其反应机制以及它们随中心元素和取代基的电子和空间特征而变化的方式。我们研究的大多数分子都是高度反应性的瞬态物种，我们使用脉冲激光诱导的光化学反应产生，并使用快速时间分辨的紫外-可见光谱直接检测和监测。 我们的部分工作涉及研究含有这些功能的稳定分子，这些分子可以提前制备;它们的（通常快速）反应通过停流动力学（另一种快速时间分辨光谱方法）进行研究。我们的工作在简单取代的二价和多重键合衍生物的机械行为之间架起了桥梁，理论可以高精度地解决，而空间位阻是合成化学家的主要兴趣。 这些类型的分子在合成和材料化学中具有巨大的应用潜力，并且还与硅和锗半导体表面的化学有关，适当取代的衍生物可作为小分子模型。发展这些物种的化学在各种结构的情况下，在各种实验条件下，和产生它们的光化学反应的机制和范围的详细了解，是重要的合成和材料化学的新战略的发展是基于这些物种的化学。 我们的工作为化学科学学生提供了肥沃的培训基地，他们代表了下一代高素质的加拿大科学家。