title: Protic conversion of nitrile into azavinylidene complexes of rhenium, a mechanistic theoretical study.
abstract: The mechanism of the protonation of the rhenium nitrile chloro-complexes [ReCl(NCCH3)(PH3)4] (2), taken as models of the real systems [ReCl(NCR)(dppe)(2)] (dppe = Ph2PCH2CH2PPh2), leading to the azavinylidene products [ReCl(NC(H)CH3)(PH3)4]+ (3) was investigated by theoretical methods at the B3LYP level of theory. Electrostatic and molecular orbital arguments and thermodynamic, kinetic, and steric factors are analyzed and indicate that the chlorine atom is the most probable site of the initial proton attack, although the direct protonation of the nitrile carbon atom is also possible as a concurrent process. For the cis-isomer of 2, the initially formed chloro-protonated species cis-[Re(ClH)(NCCH3)(PH3)4]+ further converts to the azavinylidene cis-3 via either an acid-independent 1,4-proton shift or an acid-base catalyzed pathway involving a second protonation of the nitrile carbon atom to give cis-[Re(ClH)(NC(H)CH3)(PH3)4]2+ followed by elimination of the proton from the chlorine atom.
authors.affiliation: Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Av. Rovisco Pais, 1049-001 Lisbon, Portugal.
authors.forename: Maxim L
authors.initials: ML
authors.lastname: Kuznetsov
authors.forename: Alexey A
authors.initials: AA
authors.lastname: Nazarov
authors.forename: Armando J L
authors.initials: AJ
authors.lastname: Pombeiro