American Chemical Society
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Synthesis and Structure of Cationic Triruthenium Complexes Containing an Oxametallacycle:  Reversible Carbon−Oxygen Bond Formation and Scission on an Electron-Deficient Triruthenium Plane

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journal contribution
posted on 2020-04-02, 17:32 authored by Makoto Moriya, Toshiro Takao, Hiroharu Suzuki
A trimetallic μ-hydroxo complex, [(Cp*Ru)3(μ-OH)(μ3-CH)(μ3131-CHCMeCH)]2+ (6), was obtained by the reaction of an equilibrating mixture of the dicationic tris(μ-carbene) complexes [(Cp*Ru)33-CH)(μ-H)(μ33-C3MeH2)]2+ (4a and 4b) with water. Treatment of the μ-hydroxo complex with a base affords a novel μ3-2-oxa-4-methylruthenacyclopentenyl complex, [(Cp*Ru)33-CH){μ3-OC(H)C(Me)CH−}]2+ (8), as a result of reductive C−O bond coupling. Complex 8 underwent unprecedented isomerization to a μ3-2-oxa-3-methylruthenacyclopentenyl complex, [(Cp*Ru)33-CH){μ3-O-C(Me)C(H)CH−}]2+ (8), containing a methyl group at the 3-position of the oxaruthenacycle moiety upon heating, which involves sequential C−O bond cleavage and re-formation via the formation of a transient μ-oxo complex having a μ33-C3 ring on the triruthenium plane.