Transition metal hydride and main-group element complexes in new ligand environments

过渡金属氢化物是具有金属-氢键的化合物，由于其与整个催化工业氢化物转移过程（包括商品化学品和精细化学品的生产）以及在实验室应用中制造大量衍生物的相关性，因此在化学中不可或缺。工业催化剂主要是多相的，反应中间体的性质定义不明确，而实验室均相催化剂的特征是非常明确的反应位点（通常基于一个，两个或几个金属中心），由可控电子和空间性质的辅助基团支撑。直到最近，绝大多数已建立的氢化物络合物仅基于丰富的膦、羰基和聚烯烃配体环境，而对由新一代氮基配体支持的氢化物络合物的反应性知之甚少。这种新的配体和配体组合现在已经很好地建立，但几乎仅在均相烯烃聚合催化的狭窄范围内。氢化物化学研究的另一个重要场所集中在理解催化过程中金属配位层中键断裂/形成过程的性质。为此，分离和研究具有“冻结”配体间相互作用的复合物是极其重要的。氢化物化合物的域中发现的非经典interligand键合的现象，首先，在二氢配合物和CH-agostic配合物，第二，在其他σ-配合物。这使科学家们首次能够模拟金属介导的小分子转化中的关键步骤。本项目的主要目的是制备和研究新型的具有潜在催化活性的过渡金属氢化物配合物，并通过研究具有“冻结”的非经典配体间相互作用的配合物来了解它们的活性。

Transition metal hydrides, compounds with a metal-hydrogen bond, are indispensable in chemistry due to their relevance to the whole range of catalytic industrial hydride transfer processes, including the production of both commodity chemicals and fine chemicals, and in laboratory applications to make a large range of derivatives. Whereas industrial catalysts are primarily heterogeneous with a poorly defined nature of reactive intermediates, laboratory homogeneous catalysts feature very well-defined reactive sites (usually based on one, two or few metal centres) supported by ancillary groups of controllable electronic and steric properties. Until very recently, the vast majority of established hydride complexes were based solely on the abundant phosphine, carbonyl, and polyolefin ligand environments, while relatively little is known about the reactivity of hydride complexes supported by new generations of nitrogen-based ligands. Such new ligands and ligand combinations are now well established, but almost exclusively in the narrow context of homogeneous olefin polymerization catalysis.Another significant venue of research in hydride chemistry is focused on understanding the nature of bond rupture/formation processes in the coordination sphere of metals during catalysis. To this end, the isolation and study of complexes with "frozen" interligand interactions is extremely important. The hydride compounds were the domain in which the phenomenon of nonclassical interligand bonding was discovered, first, in dihydrogen complexes and in CH-agostic complexes and, second, in other sigma-complexes. This allowed scientists, for the first time, to model the key steps in the metal-mediated transformations of small molecules. In particular, our group pioneered the investigations of interligand hypervalent interactions and discovered new families of complexes featuring stretched beta-Si-H agostic interactions.The fundamental aim of this project is to prepare and study new types of potentially catalytically active transition metal hydride complexes and understand their activity through the study of complexes with "frozen" nonclassical interligand interactions.