2024-05-082024-05-082023G. Alférez, M., Moreno Díaz, J.J., Gaona, M.A., Maya Díaz, C.M. y Campos, J. (2023). Ligand Postsynthetic Functionalization with Fluorinated Boranes and Implications in Hydrogenation Catalysis. ACS Catalysis, 13 (24), 16055-16056. https://doi.org/10.1021/acscatal.3c02764.2155-5435https://hdl.handle.net/11441/157966The incorporation of boron functionalities into transition-metal catalysts has become a promising strategy to improve catalytic performance, although their synthesis typically entails the preparation of sophisticated bifunctional ligands. We report here the facile and direct postsynthetic functionalization of rhodium(I) compound [(η5-C9H7)Rh(PPh3)2] (1) by treatment with perfluorinated boranes. Borane addition to 1 results in an unusual C(sp2)-H hydride migration from the indenyl ligand to the metal with the concomitant formation of a C-B bond. In the case of Piers’ borane [HB(C6F5)2], this is followed by a subsequent hydride migration that leads to an unprecedented 1,2-hydrogen shift reminiscent of Milstein’s cooperative dearomatization pathways. Computational investigations provide a mechanistic picture for the successive hydride-migration steps, which enriches the non-innocent chemistry of widespread indenyl ligands. Moreover, we demonstrate that the addition of Piers’ borane is highly beneficial for catalysis, increasing catalyst efficiency up to 3 orders of magnitude.application/pdf12 p.engAtribución 4.0 Internacionalhttp://creativecommons.org/licenses/by/4.0/HydrogenationLigand functionalizationPendant boraneRhodiumσ-borane complexinfo:eu-repo/semantics/articleinfo:eu-repo/semantics/openAccess10.1021/acscatal.3c02764