title: C-NH2 bond formation mediated by iridium complexes.
abstract: In the presence of phosphanes (PR3 ), the amido-bridged trinuclear complex [{Ir(μ-NH2 )(tfbb)}3 ] (tfbb=tetrafluorobenzobarrelene) transforms into mononuclear discrete compounds [Ir(1,2-η(2) -4-κ-C12 H8 F4 N)(PR3 )3 ], which are the products of the CN coupling between the amido moiety and a vinylic carbon of the diolefin. An alternative synthetic approach to these species involves the reaction of the 18 e(-) complex [Ir(Cl)(tfbb)(PMePh2 )2 ] with gaseous ammonia and additional phosphane. DFT studies show that both transformations occur through nucleophilic attack. In the first case the amido moiety attacks a diolefin coordinated to a neighboring molecule following a bimolecular mechanism induced by the highly basic NH2 moiety; the second pathway involves a direct nucleophilic attack of ammonia to a coordinated tfbb molecule.
authors.affiliation: Instituto de Síntesis Química y Catálisis Homogénea ISQCH, Departamento de Química Inorgánica, Universidad de Zaragoza-CSIC, C/Pedro Cerbuna, 12, 50009 Zaragoza (Spain).
authors.forename: Inmaculada
authors.initials: I
authors.lastname: Mena
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Casado
authors.forename: Víctor
authors.initials: V
authors.lastname: Polo
authors.forename: Pilar
authors.initials: P
authors.lastname: García-Orduña
authors.forename: Fernando J
authors.initials: FJ
authors.lastname: Lahoz
authors.forename: Luis A
authors.initials: LA
authors.lastname: Oro
keywords: CN formation; NH activation; amido transfer; ammonia; iridium