title: Deprotonation induced ligand-to-metal electron transfer: synthesis of a mixed-valence Rh(-I,I) dinuclear compound and its reaction with dioxygen.
abstract: Treatment of bis(2-picolyl)amine (bpa) with [{Rh(nbd)(mu-OMe)}2] leads to the unexpected and unique redox asymmetric dinuclear Rh-I,Rh+I complex [{Rh(nbd)}2(bpa-2H)] (2) with a pi-coordinating imine bound to a tetrahedral low valent rhodate(-I). Mono-oxygenation of the deprotonated bpa ligand in 2 by O2 leads to the mononuclear carboxamido complex [Rh(nbd)(bpam-H)] (3) (bpam = N-(2-picolyl)picolinamide). The second O atom of O2 ends up as a hydroxo fragment in [{Rh(nbd)(mu-OH)}2].
authors.affiliation: Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, E-50009 Zaragoza, Spain. ctejel@unizar.es
authors.forename: Cristina
authors.initials: C
authors.lastname: Tejel
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Ciriano
authors.forename: M Pilar
authors.initials: MP
authors.lastname: del Río
authors.forename: Fieke J
authors.initials: FJ
authors.lastname: van den Bruele
authors.forename: Dennis G H
authors.initials: DG
authors.lastname: Hetterscheid
authors.forename: Nearchos
authors.initials: N
authors.lastname: Tsichlis i Spithas
authors.forename: Bas
authors.initials: B
authors.lastname: de Bruin