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  “Canopy Catalysts” for Alkyne Metathesis: Molybdenum Alkylidyne Complexes with a Tripodal Ligand Framework

Hillenbrand, J., Leutzsch, M., Yiannakas, E., Gordon, C. P., Wille, C., Nöthling, N., et al. (2020). “Canopy Catalysts” for Alkyne Metathesis: Molybdenum Alkylidyne Complexes with a Tripodal Ligand Framework. Journal of the American Chemical Society, 142(25), 11279-11294. doi:10.1021/jacs.0c04742.

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 Creators:
Hillenbrand, Julius1, Author           
Leutzsch, Markus2, Author           
Yiannakas, Ektoras1, Author           
Gordon, Christopher P.3, Author
Wille, Christian1, Author           
Nöthling, Nils4, 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 Zürich, Vladimir-Prelog-Weg 1-5, 8093 Zürich, Switzerland, ou_persistent22              
4Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445625              

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 Abstract: A new family of structurally well-defined molybdenum alkylidyne catalysts for alkyne metathesis is presented, which is distinguished by a tripodal trisilanolate ligand architecture. Complexes of type 1 combine the virtues of previous generations of silanolate-based catalysts with a significantly improved functional group tolerance. They are easy to prepare on scale; the modularity of the ligand synthesis allows the steric and electronic properties to be fine-tuned and hence the application profile of the catalysts to be optimized. This opportunity is manifested in the development of catalyst 1f, which is as reactive as the best ancestors but exhibits an unrivaled scope. The new catalysts work well in the presence of unprotected alcohols of all sorts and various other protic groups. The chelate effect entails even a certain stability towards water, which marks a big leap forward in metal alkylidyne chemistry in general. At the same time, they tolerate many donor sites, including basic nitrogen and numerous heterocycles. This aspect is substantiated by applications to polyfunctional (natural) products. A combined spectroscopic, crystallographic and computational study provides insights into structure and electronic character of complexes of type 1. Particularly informative are a DFT-based chemical shift tensor analysis of the alkylidyne carbon atom as well as 95Mo NMR spectroscopy; this analytical tool had been rarely used in organometallic chemistry before but turns out to be a sensitive probe that deserves more attention. The data show that the podand ligands render a Mo-alkylidyne a priori more electrophilic than analogous monodentate triarylsilanols; proper ligand tuning, however, allows the Lewis acidity as well as the steric demand about the central atom to be adjusted to the point that excellent performance of the catalyst is ensured.

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Language(s): eng - English
 Dates: 2020-04-302020-05-282020-06-24
 Publication Status: Published in print
 Pages: 16
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.0c04742
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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 142 (25) Sequence Number: - Start / End Page: 11279 - 11294 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870