Molecules (Jul 2012)
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 Me<sub>3</sub>SiN<sub>3</sub> (TMSN<sub>3</sub>), 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 TMSN<sub>3</sub> at room temperature produced <em>N</em>-coordinated ruthenium nitrile complexes <strong>3</strong>. Unlike the reaction of cyclopropenylruthenium complexes with TMSN<sub>3</sub>, 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 PPh<sub>3</sub> ligands with TMSN<sub>3</sub>. 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<sub>3</sub> afforded different products.
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