Decomposition of Olefin Metathesis Catalysts by Brønsted Base: Metallacyclobutane Deprotonation as a Primary Deactivating Event

Brønsted bases
of widely varying strength are shown to decompose
the metathesis-active Ru intermediates formed by the second-generation
Hoveyda and Grubbs catalysts. Major products, in addition to propenes,
are base·HCl and olefin-bound, cyclometalated dimers [RuCl­(κ2-H2IMes−H)­(H2CCHR)]2 Ru-3. These are generated in ca. 90% yield on
metathesis of methyl acrylate, styrene, or ethylene in the presence
of either DBU, or enolates formed by nucleophilic attack of PCy3 on methyl acrylate. They also form, in lower proportions,
on metathesis in the presence of the weaker base NEt3.
Labeling studies reveal that the initial site of catalyst deprotonation
is not the H2IMes ligand, as the cyclometalated structure
of Ru-3 might suggest, but the metallacyclobutane (MCB)
ring. Computational analysis supports the unexpected acidity of the
MCB protons, even for the unsubstituted ring, and by implication,
its overlooked role in decomposition of Ru metathesis catalysts.