Reactivity of ruthenium vinylidene complexes containing indenyl/dppe ligands and unsaturated bonds at cδ with trimethylsilyl azide

This study presents a new reaction of cationic vinylidene complexes with Me ₃SiN ₃ (TMSN ₃), which yields N-coordinated nitrile complexes 3. Treatment of a ruthenium acetylide precursor containing indenyl and dppe ligands with a series of organic halides produced the corresponding vinylidene complexes 2 in good yield. Further reaction of 2 with TMSN ₃ at room temperature produced N-coordinated ruthenium nitrile complexes 3. Unlike the reaction of cyclopropenylruthenium complexes with TMSN ₃, which yielded different products depending on the substituent at Cγ, the vinylidene complexes containing unsaturated bonds at Cδyielded similar N-coordinated nitrile complexes. This transformation did not seemingly occur in the reaction of ruthenium vinylidene complexes taining Cp and PPh ₃ ligands with TMSN ₃. Deprotonation of these vinylidene complexes yielded cyclopropenyl or thermodynamic furylruthenium complexes, depending on the substitute at Cγ. Subsequent reactions of the cyclopropenyl or furylruthenium complexes with TMSN ₃ afforded different products.