High-valent iron complexes with bispidine ligands: Analysis of spin states and reaction channels

具有双吡啶配体的高价铁配合物：自旋态和反应通道的分析

• 批准号: 282929485
• 负责人: Professor Dr. Peter Comba
• 金额: --
• 依托单位: Anorganisch-Chemisches Institut
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/282929485?language=en
• 关键词: valent; iron; complexes; bispidine; ligands

High-valent metal-oxo complexes are relevant in biological systems, in the environment and in processes of industrial importance. With bispidine ligands, we have established and thoroughly studied a platform that enables us to quench and study spectroscopically important intermediates and to vary important parameters such as the coordination geometry, the spin state and the driving force, i.e. the redox potential. We believe that this will enable us to understand how one can switch between specific reaction channels and how important properties (structure, spin, driving force, reactivity) are correlated to each other.An important part of the project is to determine how the driving force and the reactivity depend on the spin state. We believe that we can prepare ferryl systems which at room temperature are close to the spin crossover. We then will determine the redox potential and reactivity at the high-spin (S=2) and intermediate-spin (S=1) states. In addition, we propose systems which should get the so far unknown S=0 state accessible. It will be of great interest to see what redox potential and reactivity such a species has.Another important and not well enough studied point is the basicity of the oxo group. An important species in this context is the tautomer of the metal-oxo-aqua complex, i.e. the dihydroxo complex FeIV(OH)22+ that we have proposed a few years ago and from which we now have preliminary UV-vis-NIR spectra.The experimental studies of our project will be combined with quantum chemical studies done in our group. This combination will allow us to thoroughly interpret the spectroscopic properties as well as thermodynamics and reactivities.

高价金属-氧配合物与生物系统、环境和具有重要工业意义的过程相关。通过双吡啶配体，我们建立并深入研究了一个平台，使我们能够猝灭和研究光谱上重要的中间体，并改变重要参数，如配位几何、自旋状态和驱动力，即氧化还原电位。我们相信，这将使我们能够理解如何在特定的反应通道之间切换以及重要的属性（结构、自旋、驱动力、反应性）如何相互关联。该项目的一个重要部分是确定驱动力和反应性如何依赖于自旋状态。我们相信我们可以制备出在室温下接近自旋交叉的ferryl系统。然后，我们将确定高自旋 (S=2) 和中自旋 (S=1) 状态下的氧化还原电位和反应性。此外，我们提出的系统应该能够访问迄今为止未知的 S=0 状态。看看这样一个物种具有什么氧化还原电位和反应性将是非常有趣的。另一个重要但研究不够充分的点是氧代基团的碱性。在这方面的一个重要物种是金属-氧-水复合物的互变异构体，即我们几年前提出的二氢复合物FeIV(OH)22+，现在我们已经有了初步的紫外-可见-近红外光谱。我们项目的实验研究将与我们小组所做的量子化学研究相结合。这种组合将使我们能够彻底解释光谱特性以及热力学和反应性。

项目成果

Iron catalyzed demethylation of acetic acid*

• DOI: 10.1080/00958972.2018.1490414
• 发表时间: 2018-07
• 期刊: Journal of Coordination Chemistry
• 影响因子: 1.9
• 作者: P. Comba;Dieter Faltermeier;Sascha Gieger;F. Keppler;H. Schöler;M. Schroll