Journal of the American Chemical Society, Vol.130, No.18, 5844-5844, 2008
Deprotonation induced ligand-to-metal electron transfer: Synthesis of a mixed-valence Rh(-I,I) dnuclear compound and its reaction with dioxygen
Treatment of bis(2-picolyl)amine (bpa) with [{Rh(nbd)(mu-OMe))(2)] leads to unexpected and unique redox asymmetric dinuclear Rh-I, Rh+I complex [{Rh(ndb)}(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 O-2 leads to the mononuclear carboamido complex [Rh(nbd)(bpam-H)] (3) (bpam = N-(2-picolyl)picolinamide). The second () atom of O-2 ends up as a hydroxo fragment in [{Rh(nbd)(mu-OH))(2)].