Air-stable 18-electron adducts of Schrock catalysts with tuned stability constants for spontaneous release of the active species

Schrock alkylidenes are highly versatile, very active olefin metathesis catalysts, but their pronounced sensitivity to air still hinders their applications. Converting them into more robust but inactive 18-electron adducts was suggested previously to facilitate their handling. Generating the active...

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Bibliographic Details
Published in:Communications chemistry 2021-05, Vol.4 (1), p.71-71, Article 71
Main Authors: Gulyás, Henrik, Hayano, Shigetaka, Madarász, Ádám, Pápai, Imre, Szabó, Márk, Bucsai, Ágota, Martin, Eddy, Benet-Buchholz, Jordi
Format: Article
Language:English
Subjects:
639/638/77/884
639/638/77/888
639/638/911/406/939
639/638/911/406/940
Adducts
Catalysts
Chelation
Chemistry
Chemistry and Materials Science
Chemistry/Food Science
Electrons
High temperature
Lewis acid
Ligands
Metathesis
Molybdenum
Stability
Stability constants
Tungsten
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Summary:Schrock alkylidenes are highly versatile, very active olefin metathesis catalysts, but their pronounced sensitivity to air still hinders their applications. Converting them into more robust but inactive 18-electron adducts was suggested previously to facilitate their handling. Generating the active species from the inactive adducts, however, required a high-temperature Lewis acid treatment and resulted in an insoluble by-product, limiting the practicality of the methodology. Herein, we introduce an approach to circumvent the inconvenient, costly, and environmentally taxing activation process. We show that 18-electron adducts of W- and Mo-based Schrock catalysts with finite stability constants (typically K  = 200–15,000 M −1 ) can readily be prepared and isolated in excellent yields. The adducts display enhanced air-stability in the solid state, and in solution they dissociate spontaneously, hence liberating the active alkylidenes without chemical assistance. Air-sensitive molybdenum olefin metathesis catalysts are known to form stable but inactive adducts with appropriate chelating ligands, but regenerating the active catalyst requires the use of Lewis acids and vigorous conditions. Here, tuning the electron donor capacity of the ligands leads to air-stable solid adducts of tungsten and molybdenum alkylidenes that spontaneously release the active catalysts in solution.
ISSN:2399-3669
2399-3669
DOI:10.1038/s42004-021-00503-4