Reactions of Ru(CCPh)(PPh3)2Cp with silver(I): Molecular structure of [Ag{η2-PhC2[Ru(PPh3)2Cp]}2]PF6 and synthesis of a bis(vinylidene) complex

Treatment of Ru(CCPh)(PPh3)2Cp 1 with Ag[PF6] (2/1 molar ratio, in toluene) affords [Ag{η2-PhC2[Ru(PPh3)2Cp]}2]PF62, characterised by analysis, spectroscopy and a single-crystal X-ray structure determination. A similar reaction in CH2Cl2 (1/1 molar ratio) gives [{Cp(Ph3P)2Ru}CCHC6H4CPhC{Ru(PPh3)2Cp}](PF6)24 by oxidative coupling of two alkynyl-Ru radicals.

Treatment of Ru(CCPh)(PPh3)2Cp 1 with Ag[PF6] (2/1 ratio in PhMe) affords [Ag{η2-PhC2[Ru(PPh3)2Cp]}2]PF62. A similar reaction in CH2Cl2 (1/1 ratio), or of 2 with Ag[PF6], gave bis(vinylidene) [{Cp(Ph3P)2Ru}CCHC6H4CPhC{Ru(PPh3)2Cp}](PF6)24 by oxidative coupling of two alkynyl–Ru radicals.Figure optionsDownload as PowerPoint slideHighlights
► AgPF6 reacts with Ru(CCPh)(PPh3)2Cp to give the bis-η2-alkyne–Ag complex 2.
► The X-ray structure of 2 is reported.
► Loss of Ag from 2 affords a binuclear bis-vinylidene derivative.