Deprotonation induced ligand-to-metal electron transfer: synthesis of a mixed-valence Rh(-I,I) dinuclear compound and its reaction with dioxygen.
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].
Tejel
Cristina
C
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
Ciriano
Miguel A
MA
del Río
M Pilar
MP
van den Bruele
Fieke J
FJ
Hetterscheid
Dennis G H
DG
Tsichlis i Spithas
Nearchos
N
de Bruin
Bas
B