When studying the activation of 3-arylpropiolates by [TpRu(picolyl-I-R)Cl]/NaBAr4F (picolyl-I-Me = 3-methyl-1-(2-picolyl)imidazol-2-ylidene (1); picolyl-(BI)-B-Me = 3-methyl-1-(2-picolyl)benzoimidazol-2-ylidene (2)) a migratory insertion of the NHC into a ruthenium-carbon bond and an unprecedented C-N bond activation of the chelating picolyl-NHC ligand take place to give the new ruthenium metallacycles [TpRu(kappa(3)-C,N,N'-=C(Ph)-C(CH2Py)(CO2Me)(I-Me)][BAr4F] 3a and 4a and [TpRu(kappa(3)-C,N,N'-=C(4-CF3Ph)-C(CH2Py)(CO2Me)(I-Me)][BAr4F] 3b and 4b. X-ray crystal structures of 3a and 3b are reported, and a mechanistic pathway is proposed. In contrast, activation of internal alkynones by a mixture of [TpRu(picolyl-I-Me)Cl] complex (1) and NaBAr4F led to isolation and characterization of the corresponding disubstituted vinylidene complexes. Also, structures of [TpRu(picolyl-I-Me)(=CC(COR)(Ph)][BAr4F] (R = Me (6a); Ph (6b)) are reported.