X-ray spectroscopy as a probe of unique bonding interactions of importance in transition metal catalytic processes

X 射线光谱作为过渡金属催化过程中重要的独特键合相互作用的探针

• 批准号: RGPIN-2016-05453
• 负责人: Kennepohl, Pierre
• 金额: $ 1.82万
• 依托单位: University of British Columbia
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2018
• 资助国家: 加拿大
• 起止时间: 2018-01-01 至 2019-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=655329
• 关键词: ray; spectroscopy; probe; unique; bonding

The specifics of how molecules are held together and how they react depends on a fundamental understanding of their geometric and electronic structure. Using a combination of spectroscopic and computational tools, we seek to provide a detailed understanding of the electronic structure of molecules that are of particular interest due to their unique chemical properties. In this proposal, we seek to explore specific aspects of two major classes of molecular interactions in order to provide a basic framework from which we can understand their chemical behaviour and how they may be used in a number of chemical applications.***Metal π complexes are common intermediates in important academic and industrial catalytic processes. Using a range of spectroscopic approaches, we seek to clearly identify and quantify the importance of π-backbonding in defining the nature of these species. We focus our attention on a series of nickel and copper complexes such that we may exploit x-ray spectroscopic methods to quantify the bonding in these species. Importantly, we seek to correlate these findings with the reactivity of such species so that we may be able to more accurately predict the behaviour of reactive intermediates involving π interactions of this type.***Halogen bonding is an emerging class of chemical interactions that are being used extensively in the synthesis of new materials and for sensor applications. Although such interactions are typically considered to be similar to the more common hydrogen bonding, we have recently determined that these chemical bonds are closer to those observed in transition metal coordination bonds. Given their similarities, we postulate that halogen bonding may compete with coordination bonds to generate highly reactive species. We are therefore exploring the role of halogen bonding in transition metal systems to quantify its effect on both the electronic structure of coordination complexes and their reactivity.

分子如何结合在一起以及它们的反应的细节取决于对它们的几何和电子结构的基本理解。我们利用光谱和计算工具的组合，试图对由于其独特的化学特性而特别感兴趣的分子的电子结构提供详细的理解。在此提案中，我们试图探索两种主要的分子相互作用的特定方面，以提供一个基本的框架，我们可以从中了解它们的化学行为以及它们如何在许多化学应用中使用。我们使用一系列的光谱方法，试图清楚地识别和量化π-backbond在定义这些物种本质中的重要性。我们将注意力集中在一系列的镍和铜复合物上，以便我们可以利用X射线光谱方法来量化这些物种中的键。重要的是，我们试图将这些发现与此类物种的反应性相关联，以便我们可以更准确地预测与这种类型的π相互作用有关的反应性中间体的行为。****卤素键合是在新材料合成和传感器应用中广泛使用的新兴化学相互作用类别。尽管通常认为这种相互作用类似于更常见的氢键，但我们最近确定这些化学键更接近于过渡金属配位键中观察到的化学键。鉴于它们的相似性，我们假设卤素键可能会与协调键竞争以产生高反应性物种。因此，我们正在探索卤素键在过渡金属系统中的作用，以量化其对配位络合物的电子结构及其反应性的影响。