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

我们的研究项目专注于生物、环境和无机化学中涉及的重要反应中间体的几何和电子特征。广泛的光谱方法与理论方法相结合，构建了对这些中间体及其反应活性的实验有效的电子结构描述。我们开发了一种新的方法来检测和表征蛋白质环境中的硫基自由基，这使我们能够对生物中的不可反应性有新的见解。我们正在扩展这一方法，以解决有关生物环境中硫、硒和砷自由基的重要问题。此外，我们还探索了一系列与烯烃歧化反应有关的重要有机金属催化剂的电子结构。我们的初步研究已经确定了N-杂环卡宾的电子结构与作为中性给体膦的膦相比在催化方面的重要差异。我们正在探索这些差异的程度及其对均相催化中一系列重要领域的反应性的影响。

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.