Group 14 Reactive Intermediates & Organic/Organometallic Photochemistry

我们的NSERC Discovery计划专注于包含一个或多个重四元元素(硅、锗和锡)的二价和多键分子反应的快速动力学研究，以期全面了解它们的反应机理以及它们随中心元素和取代基的电子和空间特性而变化的方式。我们研究的大多数分子都是高活性的瞬变物种，我们利用脉冲激光诱导的光化学反应产生这些分子，并使用快速时间分辨UV-Vis光谱直接检测和监测。我们的部分工作包括研究包含这些功能的稳定分子，这些功能可以提前制备；它们的(通常是快速)反应是通过停流动力学来研究的，这是另一种快速的时间分辨光谱方法。我们的工作在简单取代的二价和多键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这些问题，而空间位阻的衍生物是合成化学家主要感兴趣的。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，也与硅和锗半导体表面的化学有关，适当取代的衍生物作为小分子模型。详细了解这些物种在各种结构情况和各种实验条件下的化学，以及产生这些物种的光化学反应的机理和范围，对于开发以这些物种的化学为基础的合成和材料化学的新策略是重要的。我们的工作为化学科学领域的学生提供了肥沃的培训场地，他们代表着下一代高素质的加拿大科学家。

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.