The reaction of (Ph 3P) 3RuCl 2 with 1,1-diphenyl-2-propyn-1-ol was investigated in various solvents. The reaction in thf under reflux is reported to produce the (PPh 3) 2Cl 2Ru(3-phenylindenylidene) complex ( 3) which has undergone rearrangement of the allenylidene C 3-spine. We have improved the reliability of the reported synthesis by adding acetyl chloride which converts the formed water of the reaction and thus increases the acidity of the reaction solution. Without the additive, we observed the exclusive formation of an intermediate of the transformation and identified it as dinuclear (PPh 3) 2ClRu(μ-Cl) 3(PPh 3) 2Ru C C CPh 2 complex ( 5). The reaction of (Ph 3P) 3−4RuCl 2 with 1,1-diphenyl-2-propyn-1-ol in CH 2Cl 2 or C 2H 4Cl 2 under reflux in the presence of excess conc. aqueous HCl afforded the new, neutral (PPh 3) 2Cl 3Ru C–CH CPh 2 carbyne complex ( 7), an HCl adduct of previously elusive (PPh 3) 2Cl 2Ru C C CPh 2 complex 6 in high yields. In contrast to the formation of complex 3, the reaction in a non-coordinating solvent did not afford the rearrangement of the allenylidene C 3-spine. Complex 7 was converted into complex 3 in thf under reflux under loss of a molecule HCl. Complex 7 was converted with triethylamine under loss of HCl to complex 6. Pentacoordinate complex 6 was crystallized in the presence of O-donor ligands (EtOH, MeOH and H 2O) to give hexacoordinate (PPh 3) 2Cl 2(ROH)Ru C C CPh 2 (R = H, CH 3, C 2H 5) complexes ( 9)–( 11) with the O-donor coordinating in trans-position to the allenylidene moiety. The reaction of complex 7 with 2 equiv. of 4-( N, N-dimethylamino)pyridine (DMAP) gave hexacoordinate (PPh 3) 2Cl 2(DMAP)Ru C C CPh 2complex ( 12) with one molecule DMAP also coordinating in trans-position to the allenylidene group. Methanol and acetic acid in the absence of strong bases afforded the Fischer-carbene complexes (PPh 3) 2Cl 2Ru C(OCH 3)–CH CPh 2 ( 14) and (PPh 3) 2Cl 2Ru C(OAc)–CH CPh 2 ( 15) where the nucleophile added to the α-carbon atom. The structures of complexes 5, 7, 9–11, 14, and 15 were solved via X-ray crystallography.