Abstract
The reaction of diphenylacetylene at a cationic ruthenium complex with a dppm (Ph2PCH2PPh2) ligand, [CpRu(dppm)]+, has been studied to reveal essentially for the first time the existence of an equilibrium between an η2-internal alkyne and η1-disubstituted vinylidene at a transition metal center. The reaction mixture at 70 °C for 69 h unexpectedly afforded a coupling product of diphenylacetylene and the dppm ligand, an (alkenylphosphonio)phenyl complex [CpRu{Ph2PCH2P(C6H4)Ph(η2-C(Ph)═CHPh)}]+ with the extremely rare coordination mode of κ1P,η1C,η2C,C′. The (alkenylphosphonio)phenyl complex further undergoes inversion of the coordination face of the alkene moiety at p-xylene reflux temperature. Both isomers of (alkenylphosphonio)phenyl complexes as well as the intermediary η2-internal alkyne and η1-disubstituted vinylidene complexes were fully characterized spectroscopically and crystallographically. By considering the structure of the (alkenylphosphonio)phenyl complexes obtained, the coupling reaction has been proposed to involve the attack of a phosphorus atom on the coordinated diphenylacetylene, which is in equilibrium with an η1-diphenylvinylidene ligand, and the C–H bond activation of a phenyl group on the cationic phosphorus atom leading to the products. Theoretical calculations support the proposed mechanism.
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