Spectroscopic investigations of electronic and geometric structure of reactive intermediates in chemistry and biology

化学和生物学中反应中间体的电子和几何结构的光谱研究

• 批准号: 298395-2007
• 负责人: Kennepohl, Pierre
• 金额: $ 2.7万
• 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: 2007
• 资助国家: 加拿大
• 起止时间: 2007-01-01 至 2008-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=363783
• 关键词: Spectroscopic; investigations; electronic; geometric; structure

Our research program focuses on the geometric and electronic characterisation of important reactionintermediates involved in biological, environmental, and inorganic chemistry. A wide range of spectroscopicmethods are used in conjunction with theoretical methods to construct experimentally-valid electronic structuredescriptions of these intermediates and their reactivity. We have developed a new approach to detecting andcharacterising sulfur-based radicals in protein environments, which is allowing us novel insights into theirreactivity in biology. We are extending this approach to address important questions about the sulfur, selenium,and arsenic-based radicals in biological environments. We are furthermore exploring the electronic structure ofa series of important organometallic catalysts involved in olefin metathesis. Our initial investigations havedefined important differences in the electronic structure of N-heterocyclic carbenes as compared to phosphinesas neutral donor ligands in catalysis. We are exploring the extent of these differences and their effect onreactivity in a range of areas of importance in homogeneous catalysis.

我们的研究计划着重于与生物，环境和无机化学有关的重要反应中间体的几何和电子表征。广泛的光谱方法与理论方法结合使用，以构建这些中间体的实验性电子结构构图及其反应性。我们已经开发了一种新的方法来检测蛋白质环境中的基于硫的自由基，这使我们可以对生物学的反应性进行新颖的见解。我们正在扩展这种方法，以解决有关生物环境中硫，硒和基于砷的自由基的重要问题。我们还在探索一系列参与烯烃元理解的重要有机金属催化剂的电子结构。我们的初步研究定义了与中性供体配体在催化中相比，N-杂环碳烯的电子结构的重要差异。我们正在探索这些差异的程度及其在同质催化中重要的领域的影响。