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


ABSTRACT: 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.

SUBMITTER: Gulyas H 

PROVIDER: S-EPMC9814263 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

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

Gulyás Henrik H   Hayano Shigetaka S   Madarász Ádám Á   Pápai Imre I   Szabó Márk M   Bucsai Ágota Á   Martin Eddy E   Benet-Buchholz Jordi J  

Communications chemistry 20210519 1


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  ...[more]

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