Taming the Chlorine Radical: Enforcing Steric Control over Chlorine-Radical-Mediated C-H Activation.
J Am Chem Soc
; 144(3): 1464-1472, 2022 01 26.
Article
in En
| MEDLINE
| ID: mdl-35020391
ABSTRACT
Chlorine radicals readily activate C-H bonds, but the high reactivity of these intermediates precludes their use in regioselective C-H functionalization reactions. We demonstrate that the secondary coordination sphere of a metal complex can confine photoeliminated chlorine radicals and afford steric control over their reactivity. Specifically, a series of iron(III) chloride pyridinediimine complexes exhibit activity for photochemical C(sp3)-H chlorination and bromination with selectivity for primary and secondary C-H bonds, overriding thermodynamic preference for weaker tertiary C-H bonds. Transient absorption spectroscopy reveals that Cl· remains confined through formation of a Cl·|arene complex with aromatic groups on the pyridinediimine ligand. Furthermore, photocrystallography confirms that this selectivity arises from the generation of Cl· within the steric environment defined by the iron secondary coordination sphere.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
J Am Chem Soc
Year:
2022
Type:
Article
Affiliation country:
United States