Proton-assisted activation of a MnIII-OOH for aromatic C-H hydroxylation through a putative [MnVO] species

Sikha Gupta; Parkhi Sharma; Khyati Jain; Bittu Chandra; Sharath Chandra Mallojjala; Apparao Draksharapu

doi:10.1039/d4cc00798k

Proton-assisted activation of a Mn^III-OOH for aromatic C-H hydroxylation through a putative [Mn^VO] species

Chem Commun (Camb). 2024 Jun 20;60(51):6520-6523. doi: 10.1039/d4cc00798k.

Authors

Sikha Gupta¹, Parkhi Sharma¹, Khyati Jain¹, Bittu Chandra², Sharath Chandra Mallojjala³, Apparao Draksharapu¹

Affiliations

¹ Southern Laboratories-208A, Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur-208016, India. [email protected].
² Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA.
³ Department of Chemistry, Binghamton University, Binghamton, New York 13902, USA. [email protected].

PMID: 38836330
DOI: 10.1039/d4cc00798k

Abstract

Adding HClO₄ to [(BnTPEN)Mn^III-OO]⁺ in MeOH generates a short-lived Mn^III-OOH species, which converts to a putative Mn^VO species. The potent Mn^VO species in MeCN oxidizes the pendant phenyl ring of the ligand in an intramolecular fashion. The addition of benzene causes the formation of (BnTPEN)Mn^III-phenolate. These findings suggest that high valent Mn species have the potential to catalyze challenging aromatic hydroxylation reactions.