The reaction of Ru(Me(2)bipy)(PPh3)(2)Cl-2 1 with terminal alkynes HCCR in the presence of TIPF6 leads to the formation of the vinylidene compounds [Ru(Me(2)bipy)(PPh3)(2)Cl(=C=CHR)][PF6] (2) (2a, R = Bu-t; 2b, R = p-C6H4-Me; 2c, R = Ph). These compounds decompose in oxygenated solution to form the carbonyl compound [Ru(Me(2)bipy)(PPh3)(2)Cl(CO)][PF6] (3), and may be deprotonated by K2CO3 to give the ruthenium(II) terminal acetylide compounds Ru(Me(2)bipy)(PPh3)(2)Cl(CdropC-R) (4) (4a, R = Bu-t; 4b, R = p-C6H4-Me; 4c, R = Ph). Cyclic voltammetry shows that 2a-c may also be reductively dehydrogenated to form 4a-c. 4a-c are readily oxidized to their ruthenium(III) analogues [4a](+)-[4c](+), and the changes seen in their UV/visible spectra upon performing this oxidation are analyzed. These show that whereas the UV/visible spectra of 4a-c show MLCT bands from the ruthenium atom to the bipyridyl ligand, those of [4a](+)-[4c](+) contain LMCT bands originating on the acetylide ligands. This is in agreement with the IR and ESR spectra of [4a](+)-[4c](+). The X-ray crystal structures of the redox pair 4a and [4a][PF6] have been determined, allowing the bonding within the metal-acetylide unit to be analyzed, and an attempt is made to determine Lever electrochemical parameters (E-L) for the vinylidene and acetylide ligands seen herein. Room temperature luminescence measurements on 4a-c show that the compounds are not strongly emissive.