This study presents a new reaction of cationic vinylidene complexes with Me3SiN3 (TMSN3), 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 TMSN3 at room temperature produced N-coordinated ruthenium nitrile complexes 3. 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 Cδ yielded similar N-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.

Facile ligand substitution is observed when the ruthenium chloride complex [Ru(η5-C9H7)Cl(PPh3)2] is treated with 1,4-bis­(diphenyl­phosphan­yl)butane in refluxing toluene yielding the title compound, [Ru(C9H7)Cl(C28H28P2)]. The RuII atom has a typical piano-stool coordination, defined by the indenyl ligand, one Cl atom and two phosphanyl P atoms. The Ru—P bond lengths are 2.2502 (9) and 2.2968 (8) Å.

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