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  183W NMR Spectroscopy Guides the Search for Tungsten Alkylidyne Catalysts for Alkyne Metathesis

Hillenbrand, J., Leutzsch, M., Gordon, C. P., Copéret, C., & Fürstner, A. (2020). 183W NMR Spectroscopy Guides the Search for Tungsten Alkylidyne Catalysts for Alkyne Metathesis. Angewandte Chemie International Edition, 59(48), 21758-21768. doi:10.1002/anie.202009975.

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anie202009975-sup-0001-misc_information-1.pdf (Supplementary material), 13MB
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 Creators:
Hillenbrand, Julius1, Author           
Leutzsch, Markus2, Author           
Gordon, Christopher P.3, Author
Copéret, Christophe3, Author
Fürstner, Alois1, Author           
Affiliations:
1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              
2Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445623              
3Department of Chemistry and Applied Biosciences, ETH ZürichVladimir-Prelog-Weg 1–5, 8093 Zürich, Switzerland, ou_persistent22              

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Free keywords: ligand design; metathesis; NMR spectroscopy; structure elucidation; tungsten
 Abstract: Triarylsilanolates are privileged ancillary ligands for molybdenum alkylidyne catalysts for alkyne metathesis but lead to disappointing results and poor stability in the tungsten series. 1H,183W heteronuclear multiple bond correlation spectroscopy, exploiting a favorable 5J‐coupling between the 183W center and the peripheral protons on the alkylidyne cap, revealed that these ligands upregulate the Lewis acidity to an extent that the tungstenacyclobutadiene formed in the initial [2+2] cycloaddition step is over‐stabilized and the catalytic turnover brought to a halt. Guided by the 183W NMR shifts as a proxy for the Lewis acidity of the central atom and by an accompanying chemical shift tensor analysis of the alkylidyne unit, the ligand design was revisited and a more strongly π‐donating all‐alkoxide ligand prepared. The new expanded chelate complex has a tempered Lewis acidity and outperforms the classical Schrock catalyst, carrying monodentate tert‐butoxy ligands, in terms of rate and functional‐group compatibility.

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Language(s): eng - English
 Dates: 2020-08-212020-07-202020-08-212020-08-212020-11-23
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/anie.202009975
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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: 59 (48) Sequence Number: - Start / End Page: 21758 - 21768 Identifier: ISSN: 1433-7851
CoNE: https://pure.mpg.de/cone/journals/resource/1433-7851