Building Square Planar Cobalt (II) Complexes via Sodium Mediated Cobaltation of Fluoroarenes
Alessandra Logallo, Manting Mu, Max García‐Melchor, Eva Hevia
Abstract
Abstract While cobalt complexes have already shown their potential for C−H and C−F bond activation of fluoroarenes, their reactivity as metalating agents via Co−H exchange towards these substrates has not been explored. Herein, we report a Co(HMDS) 2 [HMDS=N(SiMe 3 ) 2 ] system which, when synergistically enhanced via sodium amide Na(HMDS) mediation, can render chemo‐ and regioselective cobaltation of a series of fluoroarenes to produce a new class of homoleptic square planar [Na 2 CoAr 4 ] complexes. Density functional theory calculations elucidate the key roles of the Na/Co counterparts in a stepwise sodiation/cobalt transmetalation process, leading to this novel C−H metalation. Depending on the reaction stoichiometry, this process can occur inter‐ or intramolecularly, furnishing transient [NaCo(HMDS) 2 Ar] intermediates which can undergo ligand rearrangement to afford [Na 2 CoAr 4 ] with concomitant formation of Co(HMDS) 2 and [NaCo(HMDS) 3 ].