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Substrate-Mediated Deactivation Of A Ru(PTBu2nBn2) Cooperative Complex, John Paul J. Bow, Paul D. Boyle, Johanna M. Blacquiere

Chemistry Publications

Ligand design for metal-ligand cooperative (MLC) catalysis is inherently more complex than that for traditional non-cooperative ligands. The basicity, sterics and structure of the acid/base group in MLC proton-transfer (PT) complexes, for instance, undoubtedly influence catalyst performance. Herein, we evaluate the highly tunable PR2NR′2 (1,5-R′-3,7-R-1,5-diaza-3,7-diphosphacyclooctane) ligand family for the first time in an organic transformation. With [Ru(Cp)(PtBu2NBn2)(MeCN)][PF6] as the catalyst, no turnover was observed in the anti-Markovnikov hydration of alkynes, a known PT MLC reaction. Treatment of the cooperative complex with phenylacetylene affords a vinylammonium product in which the pendant nitrogen atom of the PtBu2NBn2 ligand forms a Lewis acid-base …