title: The addition of bromine and iodine to palladacyclopentadienyl complexes bearing bidentate heteroditopic P-N spectator ligands derived from differently substituted quinolinic frames. The unexpected evolution of the reaction.
abstract: We have synthesized two palladacyclopentadienyl derivatives bearing bidentate ligands heteroditopic 8-(diphenylphosphino)quinoline or 8-(diphenylphosphino)-2-methylquinoline. We have reacted the palladacyclopentadienyl complexes with Br2 and I2 to gain clues on the formation mechanism of the corresponding σ-butadienyl derivatives. We were able to obtain the pure σ-butadienyl derivative only in the case of Br2 reacting with the palladacyclopentadienyl complex bearing the unsubstituted quinoline. However, an equilibrium mixture of the σ-butadienyl and a novel zwitterionic species was obtained when the same complex reacts with I2. Furthermore, we have obtained exclusively an unprecedented zwitterionic complex when I2 reacts with the palladacyclopentadienyl complex bearing the substituted quinoline and a different ratio of an equilibrium mixture of σ-butadienyl and the zwitterionic species when the latter derivative reacts with Br2. The solid state structures of one σ-butadienyl complex and of the two novel zwitterionic derivatives were determined and an interpretation of the observed reactivity based on kinetic data and a computational study has been suggested.
authors.affiliation: Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari, Venice, Italy. cano@unive.it.
authors.forename: Luciano
authors.initials: L
authors.lastname: Canovese
authors.forename: Fabiano
authors.initials: F
authors.lastname: Visentin
authors.forename: Thomas
authors.initials: T
authors.lastname: Scattolin
authors.forename: Claudio
authors.initials: C
authors.lastname: Santo
authors.forename: Valerio
authors.initials: V
authors.lastname: Bertolasi