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