Deprotonation Induced Ligand-to-Metal Electron Transfer: Synthesis of a Mixed-Valence Rh(−I,I) Dinuclear Compound and Its Reaction with Dioxygen
Journal of the American Chemical Society2008Vol. 130(18), pp. 5844–5845
Citations Over TimeTop 10% of 2008 papers
Cristina Tejel, Miguel A. Ciriano, M. Pilar del Rı́o, Fieke J. van den Bruele, Dennis G. H. Hetterscheid, N.T.I. Spithas, Bas de Bruin
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].
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