Ligand Postsynthetic Functionalization with Fluorinated Boranes and Implications in Hydrogenation Catalysis.

The 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 [(η 5 -C 9 H 7 )Rh(PPh 3 ) 2 ] ( 1 ) by treatment with perfluorinated boranes. Borane addition to 1 results in an unusual C(sp 2 )-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(C 6 F 5 ) 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.