title: Solvent-assisted new reaction pathways for the (THF)W(CO)5-promoted endo- and exo-cycloisomerization of 4-pentyn-1-ol: a theoretical investigation.
abstract: New solvent-assisted mechanistic routes were located for the (THF)W(CO)5-promoted endo- and exo-cycloisomerization of 4-pentyn-1-ol using the B3LYP/6-31G (with the LANL2DZ relativistic pseudopotential for W) theory level. A mixed model was used by explicitly including a THF molecule as a component of the reactive system and taking into account the effect of bulk solvent by means of the PCM-UAHF method. This THF molecule plays a crucial role by making the endo route leading to the cyclic carbene complex the most favorable one because of an important catalytic effect. These new mechanisms allow a satisfactory rationalization of experimental facts.
authors.affiliation: Departamento de Química Física y Analítica and Instituto Universitario de Química Organometálica Enrique Moles, Universidad de Oviedo, Julián Clavería, 8; E-33006 Oviedo, Spain. tsordo@uniovi.es
authors.forename: Tomás
authors.initials: T
authors.lastname: Sordo
authors.forename: Pablo
authors.initials: P
authors.lastname: Campomanes
authors.forename: Alejandro
authors.initials: A
authors.lastname: Diéguez
authors.forename: Félix
authors.initials: F
authors.lastname: Rodríguez
authors.forename: Francisco J
authors.initials: FJ
authors.lastname: Fañanás