Ligand Postsynthetic Functionalization with Fluorinated Boranes and Implications in Hydrogenation Catalysis
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https://figshare.com/articles/dataset/Ligand_Postsynthetic_Functionalization_with_Fluorinated_Boranes_and_Implications_in_Hydrogenation_Catalysis/24681465
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资源简介：
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.
创建时间：
2023-12-15
