Open AccessCatalytic Hydrodefluorination via Oxidative Addition, Ligand Metathesis, and Reductive Elimination at Bi(I)/Bi(III) Centers
Author(s) -
Yue Pang,
Markus Leutzsch,
Nils Nöthling,
Felix Katzenburg,
Josep Cornellà
Publication year - 2021
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.1c06735
Subject(s) - chemistry , reductive elimination , oxidative addition , trifluoromethanesulfonate , ligand (biochemistry) , catalytic cycle , metathesis , medicinal chemistry , catalysis , cationic polymerization , salt metathesis reaction , hydride , redox , combinatorial chemistry , photochemistry , organic chemistry , metal , biochemistry , polymer , receptor , polymerization
Herein, we report a hydrodefluorination reaction of polyfluoroarenes catalyzed by bismuthinidenes, Phebox-Bi(I) and OMe-Phebox-Bi(I). Mechanistic studies on the elementary steps support a Bi(I)/Bi(III) redox cycle that comprises C(sp 2 )-F oxidative addition, F/H ligand metathesis, and C(sp 2 )-H reductive elimination. Isolation and characterization of a cationic Phebox-Bi(III)(4-tetrafluoropyridyl) triflate manifests the feasible oxidative addition of Phebox-Bi(I) into the C(sp 2 )-F bond. Spectroscopic evidence was provided for the formation of a transient Phebox-Bi(III)(4-tetrafluoropyridyl) hydride during catalysis, which decomposes at low temperature to afford the corresponding C(sp 2 )-H bond while regenerating the propagating Phebox-Bi(I). This protocol represents a distinct catalytic example where a main-group center performs three elementary organometallic steps in a low-valent redox manifold.