Vinyl complexes of diruthenium(IV) thiolates

• Two dinuclear σ-vinyl ruthenium(IV)-thiolate alkoxide complexes were prepared.
• The synthesized complexes were characterized by X-ray crystallography.
• Cis-addition of bulky ArSH ligand to acetylide group was observed.
• The novel structure of two five-membered metallocycles linked by Ru2S2 cores is shown.

Treatment of [Et4N][RuCl4(MeCN)2] with 2,4,6-trimethylthiophenol (HSMes) in the presence of NaOMe afforded the trigonal–bipyramidal ruthenium(IV) complex [Ru(SMes)4(MeCN)] (1), which reacted with propargylic alcohols HCCCR2OH (R = Me, Et) at ambient temperature to give the novel vinyl complexes of diruthenium(IV) thiolates [(μ-SMes)Ru{η1-O,η1-C-OCR2CHC(SMes)}(SMes)]2 (R = Me 2, Et 3). The crystal structures of 2 and 3 have been determined. The Ru−Cα bond distances are 2.011(3) and 2.023(5) Å for 2 and 3, respectively.

Treatment of the trigonal–bipyramidal ruthenium(IV) complex [Ru(SMes)4(MeCN)] (1) (Mes = 2,4,6-trimethylphenyl) with substituted propargylic alcohols gave σ-vinyl dinuclear ruthenium(IV)-thiolate complexes [(μ-SMes)Ru{η1-O,η1-C-OCR2CHC(SMes)}(SMes)]2 (R = Me 2, Et 3) with two five-numbered metallacycles linked by a Ru2S2 unit.Figure optionsDownload as PowerPoint slide