Artículo
Ligand Postsynthetic Functionalization with Fluorinated Boranes and Implications in Hydrogenation Catalysis
Autor/es | G. Alférez, Macarena
Moreno Díaz, Juan José ![]() ![]() ![]() ![]() ![]() Gaona, Miguel A. Maya Díaz, Celia María ![]() ![]() ![]() ![]() ![]() ![]() ![]() Campos, Jesús |
Departamento | Universidad de Sevilla. Departamento de Química Inorgánica |
Fecha de publicación | 2023 |
Fecha de depósito | 2024-05-08 |
Publicado en |
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Resumen | 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 ... 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 [(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. |
Agencias financiadoras | Ministerio de Ciencia e Innovación (MICIN). España Junta de Andalucía Universidad de Sevilla |
Identificador del proyecto | PID2019-110856GA-I00
![]() P18-FR- 4688 ![]() US-1380849 ![]() |
Cita | G. 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. |
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