Pr Karl KIRCHNER
Institute of Applied Synthetic Chemistry, Technische Universität Wien,
Getreidemarkt 9, 1060 Wien, Austria
e-mail: karl.kirchner@tuwien.ac.at
Catalytic Applications of Mn(I) Complexes involving E-H (E=H, C, Si, B) Bond Activations
The utilization of base-metal catalysts represents an emerging field in homogeneous catalysis. Among others, manganese-based complexes were proven to be highly competitive catalysts for several (de)hydrogenation reactions.
This lecture outlines the potential of Mn(I)-carbonyl complexes for the activation of non-polar and moderately polar E-H (E = H, C, Si, B) bonds and disclose our successful approach for the utilization of complexes in the field of homogeneous catalysis.(1-4) We took advantage of the fact that Mn(I)-alkyl carbonyl complexes undergo migratory insertion of the nucleophilic alkyl ligand into the polarized CO moiety, yielding a coordinatively unsaturated acyl complex.
This involves the rational design of manganese alkyl complexes for hydrogenation reactions. Furthermore, the potential of our Mn-based catalysts in the field of hydro-functionalization reactions for carbon-carbon multiple bonds will be discussed. Our investigations unveiled novel insights in reaction pathways of the dehydrogenative silylation and silylation of alkenes and hydroboration and trans-1,2- diboration of terminal alkynes.
References
1. “Hydrogenation of Terminal Alkenes Catalyzed by Air-Stable Mn(I) Complexes Bearing an NHeterocyclic Carbene-Based PCP Pincer Ligand”, Zobernig, D. P.; Luxner, M.; Stöger, B.; Veiros, L. F.; Kirchner, K. Chem. Eur. J. 2024, 30, e202302455
2. “Manganese Alkyl Carbonyl Complexes: From Iconic Stoichiometric Textbook Reactions to Catalytic Applications”, Weber, S.; Kirchner, K. Acc. Chem. Res. 2022, 55, 2740-2751
3. “Efficient hydroboration of alkenes and trans-diboration of alkynes catalyzed by Mn(I) alkyl complexes”, Weber, S.; Zobernig, D. P.; Stöger, B.; Veiros, L. F.; Kirchner, K. Angew. Chem., Int. Ed. 2021, 60, 24488-24492.
4. “Manganese-Catalyzed Dehydrogenative Silylation of Alkenes Following two Parallel Inner-Sphere Pathways”, Weber, S.; Glavic, M.; Stöger, B.; Pittenauer, E.; Podewitz, M.; Veiros, L. F.; Kirchner, K. J. Am. Chem. Soc. 2021, 143, 17825-17832.
