Building Square Planar Cobalt (II) Complexes via Sodium Mediated Cobaltation of Fluoroarenes.
Angew Chem Int Ed Engl
; 61(49): e202213246, 2022 Dec 05.
Article
in En
| MEDLINE
| ID: mdl-36181429
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(SiMe3 )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 [Na2 CoAr4 ] 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 [Na2 CoAr4 ] with concomitant formation of Co(HMDS)2 and [NaCo(HMDS)3 ].
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Angew Chem Int Ed Engl
Year:
2022
Document type:
Article
Affiliation country:
Suiza