Cobalt catalyzed hydrogenations: Studies on the stabilization of catalytic intermediates through heteroatom-free pi-acceptor hydrocarbons

本合作项目涉及合成含不同pi-烃配体（即烯烃、芳烃、环戊二烯）的同型和异型钴配合物，及其在催化不饱和C=C-和C= x键体系加氢反应中的应用，并通过波谱（NMR、EPR、MS）、动力学（KIE、中毒）和理论（DFT）方法阐明反应机理。提出的行动将解决富电子钴配合物与简单的烯烃和芳烃配体作为活性和选择性加氢催化剂的适用性。在低氧化态下使用钴-芳烃/烯烃预催化剂在概念上不同于钴催化反应中使用高氧化钴原子和杂原子供体配体。在本项目结束时，将与文献中已知的杂原子-供体配体/金属配合物进行详细的比较，这可能有助于开发高活性加氢催化剂。

This collaborative project involves the synthesis of homoleptic and heteroleptic cobalt complexes bearing diverse pi-hydrocarbon ligands (i.e. alkenes, arenes, cyclopentadienyls), their applications to catalytic hydrogenations of unsaturated C=C- and C=X-bond systems, and the elucidation of reaction mechanisms by spectroscopic (NMR, EPR, MS), kinetic (KIE, poisoning) and theoretical (DFT) methods. The proposed actions will address the suitability of electron-rich cobalt complexes with simple alkene and arene ligands as active and selective hydrogenation catalysts. The use of cobalt-arene/alkene precatalysts in low oxidation states is conceptually different from cobalt catayzed reactions with higher oxidized cobalt atoms and heteroatom-donor ligands. At the end of this project, a detailed comparison to literature-known heteroatom-donor ligand/metal complexes will be available which may allow the development of highly active hydrogenation catalysts.