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

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.

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 Creators:
Leutzsch, Markus1, Author              
Wolf, Larry M.2, Author              
Gupta, Puneet2, Author              
Fuchs, Michael3, Author              
Thiel, Walter2, Author              
Farès, Christophe4, Author              
Fürstner, Alois3, Author              
Affiliations:
1Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445585              
2Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              
3Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              
4Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445623              

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Free keywords: alkynes;carbenes; density functional calculations; hydrogenation; NMR spectroscopy; ruthenium
 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.

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Language(s): eng - English
 Dates: 2015-07-022015-08-312015-10-12
 Publication Status: Published in print
 Pages: 6
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/anie.201506075
 Degree: -

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Title: Angewandte Chemie International Edition
  Abbreviation : Angew. Chem., Int. Ed.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 54 (42) Sequence Number: - Start / End Page: 12431 - 12436 Identifier: ISSN: 1433-7851
CoNE: https://pure.mpg.de/cone/journals/resource/1433-7851