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Formation of Ruthenium Carbenes by gem-Hydrogen Transfer to Internal Alkynes: Implications for Alkyne trans-Hydrogenation

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Leutzsch,  Markus
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Wolf,  Larry M.
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Gupta,  Puneet
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Fuchs,  Michael
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Thiel,  Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Farès,  Christophe
Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Fürstner,  Alois
Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Leutzsch, M., Wolf, L. M., Gupta, P., Fuchs, M., Thiel, W., Farès, C., et al. (2015). Formation of Ruthenium Carbenes by gem-Hydrogen Transfer to Internal Alkynes: Implications for Alkyne trans-Hydrogenation. Angewandte Chemie International Edition, 54(42), 12431-12436. doi:10.1002/anie.201506075.


Cite as: https://hdl.handle.net/11858/00-001M-0000-0028-DB51-6
Abstract
Insights into the mechanism of the unusual trans-hydrogenation of internal alkynes catalyzed by {Cp*Ru} complexes were gained by para-hydrogen (p-H2) induced polarization (PHIP) transfer NMR spectroscopy. It was found that the productive trans-reduction competes with a pathway in which both H atoms of H2 are delivered to a single alkyne C atom of the substrate while the second alkyne C atom is converted into a metal carbene. This “geminal hydrogenation” mode seems unprecedented; it was independently confirmed by the isolation and structural characterization of a ruthenium carbene complex stabilized by secondary inter-ligand interactions. A detailed DFT study shows that the trans alkene and the carbene complex originate from a common metallacyclopropene intermediate. Furthermore, the computational analysis and the PHIP NMR data concur in that the metal carbene is the major gateway to olefin isomerization and over-reduction, which frequently interfere with regular alkyne trans-hydrogenation.