Reactivity of Ruthenium Vinylidene Complexes Containing Indenyl/dppe Ligands and Unsaturated Bonds at Cd with Trimethylsilyl Azide

Abstract

This study presents a new reaction of cationic vinylidene complexes with Me₃SiN₃ (TMSN₃), which yields <em>N</em>-coordinated nitrile complexes <strong>3</strong>. Treatment of a ruthenium acetylide precursor containing indenyl and dppe ligands with a series of organic halides produced the corresponding vinylidene complexes <strong>2</strong> in good yield. Further reaction of <strong>2</strong> with TMSN₃ at room temperature produced <em>N</em>-coordinated ruthenium nitrile complexes <strong>3</strong>. Unlike the reaction of cyclopropenylruthenium complexes with TMSN₃, which yielded different products depending on the substituent at Cγ, the vinylidene complexes containing unsaturated bonds at Cd yielded similar <em>N</em>-coordinated nitrile complexes. This transformation did not seemingly occur in the reaction of ruthenium vinylidene complexes containing Cp and PPh₃ ligands with TMSN₃. 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 TMSN₃ afforded different products.

Keywords

• vinylidene
• ruthenium
• &lt;em&gt;N&lt;/em&gt;-coordinated
• cyclopropenyl
• furyl
• indenyl