Treatment of [Cp(PR 3) 2Ru(CCC 6H 4Me- p) ( 1a, R=Ph 1b, R=Me; Cp=η 5-C 5H 5) with [Cp*Ru(μ 3·Cl)] 4 (Cp*=η 5-C 5Me 5) selectively produced the novel dinuclear μ-η 1:η 6- arylethynyl complex Cp(PR 3) 2Ru(μ-η 1:η 6-CCC 6H 4Me- p)RuCp*] ( 2·Cl: 2a, R=Ph; 2b, R=Me). Protonation of 2·OTf (OTf=OSO 2CF 3) by TfOH afforded the corresponding vinylidene complex [Cp(PR 3) 2Ru(μ-η 1:η 6-CCHC 6H 4Me- p)RuCp*]·[OTf] 2 ( 3·[OTf] 2: 3a, R=Ph; 3b, R=Me), which regenerated 2·OTf upon treatment with LiBHEt 3. Reaction of 2a·Cl with I 2 and subsequent anion metathesis with AgBF 4 produced the iodovinylidene complex [Cp(PPh 3) 2Ru(μ-η 1:η 6-CCIC 6H 4Me- p)RuCp*]·[BF 4] 2 ( 4·[BF 4] 2), whereas similar treatment of 2b·PF 6 yielded the iodo/arylethynyl complex [Cp(I)(PMe 3) 2Ru(μ-η 1:η 6-CCC 6H 4Me- p)RuCp*]·[PF 6] 2 ( 5·[PF 6] 2). Substitution of one of the PPh 3 ligands in 2a·OTf proceeded under 1 atm of CO to form [Cp(PPh 3)(CO)Ru(μ-η 1:η 6-CCC 6H 4Me- p)RuCp*]·OTf ( 6·OTf). The molecular structure of 2a·PF 6 was determined by X-ray crystallography.