One interesting tool for the 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 derivatization of fluorinated olefins and aromatics at rhodium. Rhodium hydride complexes have been used to achieve the C-F activation step, but they can also serve as catalytic precursors.2,3 Very recently, the synthesis and reactivity of highly reactive Rh(I) boryl and silyl complexes was also accomplished.4 The compounds are capable for C-F activation reactions with a unique selectivity. Catalytic derivatization reactions of hexafluoropropene or pentafluoropyridine gave silyl or boryl derivatives by cleavage carbon-fluorine bonds.4,5 The conversions represent new reaction routes to highly fluorinated precursors, some of which are not accessible otherwise.6(1) H. Amii, K. Uneyama, Chem Rev. 2009  , 109, 2119; T. Braun, R. N. Perutz, Chem. Commun. 2002  , 2749; W. D. Jones, Dalton Trans. 2003  , 399; R. P. Hughes, Eur. J. Inorg. Chem. 2009  , 4591. (2) T. Braun, D. Noveski, B. Neumann, H.-G. Stammler, Angew. Chem. Int. Ed. 2002  , 41, 2745. (3) T. Braun, K. Altenh�ner, F. Wehmeier, Angew. Chem. Int. Ed. 2007  , 46, 5321. (4) M. Teltewskoi, J. A. Panetier, S. A. Macgregor, T. Braun, Angew. Chem. Int. Ed. 2010,  48, 3280. (5) T. Braun, M. Ahijado Salomon, K. Altenh�ner, M. Teltewskoi, S. Hinze, Angew. Chem. Int. Ed. 2009  , 47, 1818. (6) F. Wehmeier, T. Braun, Eur. J. Inorg. Chem. 2011  , 613.

Rhodium(I) boryl and silyl complexes for catalytic C-F bond activations

243rd National Meeting (2012)

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