RT journal article T1 Functionalized N‑Heterocyclic Carbene Nonspectator Ligands upon Internal Alkyne Activation Reactions A1 Valerga, Pedro A1 Puerta Vizcaino, María del Carmen A1 Valerga Jiménez, Pedro Sixto A2 Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica AB When studying the activation of 3-arylpropiolates by [TpRu(picolyl-RI)Cl]/NaBArF 4 (picolyl-MeI = 3-methyl-1-(2- picolyl)imidazol-2-ylidene (1); picolyl-MeBI = 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(κ3-C,N,N′- =C(Ph) =C(CH2Py)(CO2Me)(MeI)][BArF 4] 3a and 4a and [TpRu(κ3-C,N,N′-=C(4-CF3Ph) = C(CH2Py)(CO2Me)(MeI)]- [BArF 4] 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-MeI)Cl] complex (1) and NaBArF 4 led to isolation and characterization of the corresponding disubstituted vinylidene complexes. Also, structures of [TpRu(picolyl-MeI)(= CC(COR)(Ph)][BArF 4] (R = Me (6a); Ph (6b)) are reported. PB ACS Publications YR 2013 FD 2013-05 LK http://hdl.handle.net/10498/20431 UL http://hdl.handle.net/10498/20431 LA eng DS Repositorio Institucional de la Universidad de Cádiz RD 15-nov-2026