Färber Christian, Stegner Philipp, Zenneck Ulrich, Knüpfer Christian, Bendt Georg, Schulz Stephan, Harder Sjoerd
Inorganic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstrasse 1, 91058, Erlangen, Germany.
Institute of Inorganic Chemistry and Center for Nanointegration Duisburg-Essen (CENIDE), Universität Duisburg-Essen, Universitätsstrasse 5-7, 45141, Essen, Germany.
Nat Commun. 2022 Jun 9;13(1):3210. doi: 10.1038/s41467-022-30840-4.
Hydrogenation of unsaturated bonds is a key step in both the fine and petrochemical industries. Homogeneous and heterogeneous catalysts are historically based on noble group 9 and 10 metals. Increasing awareness of sustainability drives the replacement of costly, and often harmful, precious metals by abundant 3d-metals or even main group metals. Although not as efficient as noble transition metals, metallic barium was recently found to be a versatile hydrogenation catalyst. Here we show that addition of finely divided Fe, which itself is a poor hydrogenation catalyst, boosts activities of Ba by several orders of magnitude, enabling rapid hydrogenation of alkynes, imines, challenging multi-substituted alkenes and non-activated arenes. Metallic Fe also boosts the activity of soluble early main group metal hydride catalysts, or precursors thereto. This synergy originates from cooperativity between a homogeneous, highly reactive, polar main group metal hydride complex and a heterogeneous Fe surface that is responsible for substrate activation.
不饱和键的氢化是精细化工和石油化工行业中的关键步骤。传统上，均相和多相催化剂都基于第9族和第10族贵金属。对可持续性的认识不断提高，促使人们用储量丰富的3d金属甚至主族金属取代昂贵且往往有害的贵金属。尽管金属钡不如贵金属过渡金属高效，但最近发现它是一种通用的氢化催化剂。我们在此表明，添加本身是低效氢化催化剂的细分铁，可将钡的活性提高几个数量级，从而实现炔烃、亚胺、具有挑战性的多取代烯烃和未活化芳烃的快速氢化。金属铁还能提高可溶性早期主族金属氢化物催化剂或其前体的活性。这种协同作用源于均相、高反应性、极性主族金属氢化物配合物与负责底物活化的多相铁表面之间的协同作用。
