Divergent Fe-Mediated C-H Activation Paths Driven by Alkali Cations

Vincent Wowk; Alexis K Bauer; Aleksa Radovic; Lise-Marie Chamoreau; Michael L Neidig; Guillaume Lefèvre

doi:10.1021/jacsau.3c00649

Divergent Fe-Mediated C-H Activation Paths Driven by Alkali Cations

JACS Au. 2024 Jan 19;4(2):512-524. doi: 10.1021/jacsau.3c00649. eCollection 2024 Feb 26.

Authors

Vincent Wowk¹, Alexis K Bauer², Aleksa Radovic², Lise-Marie Chamoreau³, Michael L Neidig⁴, Guillaume Lefèvre¹

Affiliations

¹ CNRS, Institute of Chemistry for Life and Health Sciences, CSB2D, Chimie ParisTech, PSL University, 75005 Paris, France.
² Department of Chemistry, University of Rochester, Rochester, New York 14627, United States.
³ CNRS, Institut Parisien de Chimie Moléculaire, Sorbonne Université, F-75252 Paris, France.
⁴ Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K.

Abstract

The association of the ferrous complex Fe^IICl₂(dmpe)₂ (1) with alkali bases M(hmds) (M = Li, Na, K) proves to be an efficient platform for the activation of Ar-H bonds. Two mechanisms can be observed, leading to either Ar-Fe^II species by deprotonative ferration or hydrido species Ar-Fe^II-H by oxidative addition of transient Fe⁰(dmpe)₂ generated by reduction of 1. Importantly, the nature of the alkali cation in M(hmds) has a strong influence on the preferred path. Starting from the same iron precursor, diverse catalytic applications can be explored by a simple modulation of the M^I cation. Possible strategies enabling cross-coupling using arenes as pro-nucleophiles, reductive dehydrocoupling, or deuteration of B-H bonds are discussed.