NMR and IR Studies of Activation of Small Molecules by Organometallic Complexes

有机金属配合物活化小分子的核磁共振和红外研究

• 批准号: EP/D058031/1
• 负责人: Mike George
• 金额: $ 35.76万
• 依托单位: University of Nottingham
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2006
• 资助国家: 英国
• 起止时间: 2006 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FD058031%2F1
• 关键词: NMR; IR; Studies; Activation; Small

Most chemical reactions proceed through a series of stages, some fast and some slow. En route, there are often highly reactive species that may last a small fraction of a second at room temperature. The nature and reactivity of these species is often key to determining the final outcome of the chemical reaction. Furthermore, these short-lived species are molecules of fundamental interest in their own right which often cannot be studied by conventional techniques. Photochemical reactions can occur at low temperatures and can be initiated by lasers and this provides a very convenient method for generating highly reactive complexes. In this proposal, we will develop a new approach combining advanced spectroscopic techniques. We will irradiate samples with a laser inside the probe of a state-of-the-art nuclear magnetic resonance (NMR) spectrometer at low temperatures, so allowing us to determine the structures of new reactive molecules. In order to achieve this, we require our new complexes to be stable for a few seconds and we will use fast infrared spectroscopic measurements in order to determine the best conditions to allow these measurements. This combination of technologies exploits the latest instrumentation in a way that has never been done before. Our chemical targets will be (a) complexes of metals with carbon dioxide, important intermediates for understanding how to mitigate greenhouse gases, (b) complexes of hydrocarbons with metals, important intermediates for understanding how to convert methane to valuable products catalytically, (c) reactions of simple silicon and nitrogen compounds at transition metals, concentrating on processes in which bonds to hydrogen are broken because of their importance in catalysis; (d) complexes of transition metals with the noble gas, xenon, because of the fundamental importance of this unreactive gas.

大多数化学反应都经过一系列的阶段，有的快，有的慢。在途中，通常会有高度反应的物质，在室温下可能会持续不到一秒。这些物质的性质和反应性往往是决定化学反应最终结果的关键。此外，这些短命物种本身就是具有根本意义的分子，通常无法用传统技术进行研究。光化学反应可以在低温下发生，并且可以由激光引发，这为生成高活性配合物提供了一种非常方便的方法。在本提案中，我们将开发一种结合先进光谱技术的新方法。我们将在低温下用激光照射最先进的核磁共振（NMR）光谱仪探头内的样品，这样我们就可以确定新的反应性分子的结构。为了实现这一目标，我们要求我们的新配合物在几秒钟内保持稳定，我们将使用快速红外光谱测量来确定允许这些测量的最佳条件。这种技术组合以一种前所未有的方式利用了最新的仪器。我们的化学目标将是(a)金属与二氧化碳的配合物，这是理解如何减少温室气体排放的重要中间体；(b)碳氢化合物与金属的配合物，这是理解如何催化将甲烷转化为有价值产品的重要中间体；(c)过渡金属上简单硅和氮化合物的反应，重点研究与氢的键断裂的过程，因为它们在催化中很重要；(d)过渡金属与稀有气体氙的配合物，因为这种不活泼的气体具有根本的重要性。

项目成果

Recent advances in organometallic alkane and noble gas complexes

• DOI: 10.1351/pac-con-08-10-17
• 发表时间: 2009-09-01
• 期刊: PURE AND APPLIED CHEMISTRY
• 影响因子: 1.8
• 作者: Calladine, James A.;Vuong, Khuong Q.;George, Michael W.
• 通讯作者: George, Michael W.

2,5-Bis(p-R-arylethynyl)rho following photolysis of (eta(5)-C4H4Se)Cr(CO)(3). A picosecond and nanosecond time-resolved infrared, matrix isolation, an

(eta(5)-C4H4Se)Cr(CO)(3) 光解后生成 2,5-Bis(p-R-arylethynyl)rho。

• 发表时间: 2010
• 期刊: Angewandte Chemie International Edition
• 作者: N/a Andreas