Chemistry of open-shell metal complexes: Tuning spin density distributions between P-ligands and metals

开壳金属配合物的化学：调节 P-配体和金属之间的自旋密度分布

• 批准号: 410910747
• 负责人: Professor Dr. Rainer Streubel
• 金额: --
• 依托单位: Institut für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2018
• 资助国家: 德国
• 起止时间: 2017-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/410910747?language=en
• 关键词: Chemistry; open; shell; metal; complexes

Due to the scarcity in knowledge about metal coordination chemistry of open-shell P-ligands, this project will endeavor to achieve new fundamental insights. We want to explore oxidative SET reactions of two classes of redox-active anionic P-ligands, categorized according to the formal charge location, i.e., at phosphorus or an alpha-neighbouring heteroatom such as O or N. The ligand-centered reactions shall generate triplet radicals that possess different electron spin density distributions; the latter is addressed by the two main research lines A and B of this project. Additionally, N-O bond homolysis will be established as viable route in part B. The different reaction opportunities of such radicals shall be disclosed by varying the substitution pattern of the anionic complex precursors as well as by the nature of the employed oxidative SET reagents: organic oxidants may provide clean trapping opportunities, whereas inorganic oxidants may open entirely new pathways. The role of the metal complex fragment in the bonding of such radicals will be comparatively studied for related group 6-10 metal complexes in order to study and modulate the influence of the metal electron configuration on the spin density distribution. Intermediates will be investigated by cyclic voltammetry (collaboration with R. Boeré), EPR, NMR or IR spectroscopy at low temperatures, and theoretical support will deepen insights into the bonding (collaboration with A. Frontera and Z.-W. Qu). The long-term goal of this proposed research project is to identify fundamental aspects of interest for metal P-ligand cooperativity in redox reactions, but also help preparing for applications in radical catalysis.

由于对开壳层P-配体的金属配位化学知识的缺乏，本项目将奋进实现新的基本见解。我们想探索两类氧化还原活性阴离子P-配体的氧化SET反应，根据形式电荷位置分类，即，在磷或α-相邻杂原子如O或N上。配体为中心的反应将产生具有不同电子自旋密度分布的三重态自由基;后者由本项目的两条主要研究线A和B解决。此外，在B部分中，将N-O键均裂确定为可行途径。通过改变阴离子络合物前体的取代模式以及通过所采用的氧化SET试剂的性质，可以揭示这些自由基的不同反应机会：有机氧化剂可以提供干净的捕获机会，而无机氧化剂可以打开全新的途径。金属配合物碎片在这种自由基键合中的作用将与相关的第6-10族金属配合物进行比较研究，以研究和调节金属电子构型对自旋密度分布的影响。中间体将通过循环伏安法（与R. Boeré），EPR，NMR或IR光谱在低温下，和理论支持将加深对键合的见解（与A。弗朗特拉和Z.- W. Qu）。这个研究项目的长期目标是确定氧化还原反应中金属P-配体协同性的基本方面，同时也有助于为自由基催化的应用做准备。