An Air- and Moisture-Stable Ruthenium Pre-Catalyst for Diverse Reactivity

Gillian Mcarthur, Jamie H. Docherty, Mishra Deepak Hareram, Marco Simonetti, Inigo J. Vitorica-Yrezabal, James J. Douglas, Igor Larrosa

Research output: Contribution to journalArticlepeer-review


Versatile, efficient, and robust (pre)catalysts are pivotal in accelerating the discovery and optimisation of chemical reactions, shaping diverse synthetic fields such as cross-coupling, C-H functionalisation and polymer chemistry. Yet, their scarcity in certain domains has hindered the advancement and adoption of new applications, particularly in industrial settings. Herein, we present a highly reactive, air- and moisture-stable, ruthenium pre-catalyst [(tBuCN)5Ru(H2O)](BF4)2, featuring a key exchangeable water ligand. This versatile pre-catalyst drives an array of transformations, including late-stage C(sp2)-H arylation, primary/secondary alkylation, methylation, hydrogen/deuterium exchange,
C(sp3)-H oxidation, alkene isomerisation, and oxidative cleavage, consistently outperforming conventionally used ruthenium (pre)catalysts. The generality and applicability of this new pre-catalyst is exemplified through the potential for rapid screening and optimisation of photocatalytic reactions with a suite of in situ generated ruthenium photocatalysts containing hitherto unknown complexes, as
well as through the rapid discovery of reactivities new to ruthenium. The diverse applicability observed is suggestive of a generic platform for reaction
simplification and accelerated synthetic discovery that will enable broader applicability and accessibility to state-of-the-art ruthenium catalysis.
Original languageEnglish
JournalNature Chemistry
Publication statusAccepted/In press - 20 Feb 2024


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