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