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(3)SiN(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 Cδ yielded similar N-coordinated nitrile complexes. This transformation did not seemingly occur in the reaction of ruthenium vinylidene complexes containing 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.