Catalytic Hydrodefluorination via Oxidative Addition, Ligand Metathesis, and Reductive Elimination at Bi(I)/Bi(III) Centers | Zendy

Yue Pang | Zendy; Markus Leutzsch | Zendy; Nils Nöthling | Zendy; Felix Katzenburg | Zendy; Josep Cornellà | Zendy

Open Access

Catalytic 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 , catalysis , medicinal chemistry , cationic polymerization , salt metathesis reaction , redox , hydride , combinatorial chemistry , photochemistry , organic chemistry , metal , polymerization , biochemistry , polymer , receptor

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.

The content you want is available to Zendy users.

Already have an account? Click here to sign in.

Having issues? You can contact us here

Accelerating Research