Towards a Conceptual Transfer of Gas-Phase Ion-Chemistry into the Condensed Phase

该研究项目的目的是将气相离子化学的概念转移到凝聚相。由于两种环境的条件非常不同，这种转移不是微不足道的，到目前为止还没有得到充分的研究。相反，质谱法越来越多地用于研究溶液中的过程。因此，更深入地了解这两相的化学反应性关系是至关重要的。从这些努力中得出的一个目标是实际利用在气相实验中获得的结果。重点是小分子的活化、成键反应和氧原子转移。最终目标是发展气相激发的催化转化。为了实现这一目标，我们使用模型系统，我们在气相实验和溶液中研究其反应性。这些实验能够确定溶剂分子、反离子和附加连接对本征反应性模式的影响。其中一个目标模型系统涉及异双金属铸币-金属铂配合物。在气相实验中，裸双原子阳离子介导甲烷和氨的脱氢c - n键偶联。另一个方向是对配体交换过程的研究。在第二个资助期，重点是研究金属-氧配合物。这个方向的灵感来自于双原子过渡金属氧离子丰富的气相化学。在我们的气相模拟方法的框架中，我们希望在质谱和溶液中产生适当的协调系统。我们将研究这些系统的反应性作为协调环境的函数。

The aim of the research project is the conceptual transfer of gas-phase ion-chemistry into the condensed phase. Due to the very different conditions in both environments, such a transfer is not trivial and has not been studied sufficiently so far. Conversely, mass-spectrometric methods are increasingly used to study processes in solution. Therefore, it is crucial to gain a deeper understanding of the relationship of chemical reactivity in both phases. A goal derived from these efforts is to make practical use of the results gained in gas-phase experiments. The focus is on the activation of small molecules, bond-forming reactions, and oxygen-atom transfer. The ultimate goal is the development of gas phase-inspired catalytic transformations. Towards this goal, we use model systems, the reactivity of which we investigate both in gas-phase experiments and in solution. These experiments enable the determination of the influence of solvent molecules, counterions, and additional ligation on intrinsic-reactivity patterns. One of the targeted model systems involves heterobimetallic coinage-metal platinum-complexes. The bare diatomic cations mediate dehydrogenative C–N-bond coupling of methane and ammonia in gas-phase experiments. Another direction constitutes the investigation of ligand-exchange processes. In the second funding period, the focus is on investigations of metal-oxo complexes. This direction is inspired by the rich gas-phase chemistry of diatomic transition-metal oxo cations. In the framework of our gas-phase mimetic approach, we want to generate appropriately coordinated systems both mass-spectrometrically and in solution. We will study the reactivity of these systems as a function of the coordination environment.