One approach for a unique derivatization of fluorinated molecules is based on the C-F activation of a carbon-fluorine bond at a transition metal center. The strategy often involves the selective removal of a fluorine atom from highly fluorinated precursors, followed by functionalization reactions in the coordination sphere of the metal.1We will report on the C-F-activation and the stoichiometric or catalytic hydrodefluorination of aromatics at the binuclear rhodium complex [{Rh(�-H)(dippp)}2] (dippp = 1,3-bis(di-iso-propylphosphanyl)propane).2 [Rh(Bpin)(PEt3)3] was used to accomplish borylation reactions by C-H activation of SCF3 aromatics. However, treatment of pentafluorosulfanyl compounds with [{Rh(�-H)(dippp)}2] led in the presence of HSiEt3 to a complete defluorination at sulphur to give thiolato species.3 The degradation of SF6 by S?F activation reactions at [Rh(�-H)(dippp)]2 was achieved. An unprecedented cyclic process to convert SF6 into H2S was developed.(1) H. Amii, K. Uneyama, Chem Rev. 2009 , 109, 2119; M. Kuehnel, D. Lentz, T. Braun, Angew. Chem. Int. Ed. 2013 , 52, 3328. (2) L. Z�mostn�, M. Ahrens, T. Braun, J. Fluorine Chem. 2013 , 155, 132. (3) L. Z�mostn�, T. Braun, B. Braun, Angew. Chem. Int . Ed. 2013 , 53, 2745.

C-F, C-H, and S-F bond activations of fluorinated compounds at rhodium(I) complexes

248th National Meeting (2014)

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