Synthetic and mechanistic investigations on manganese corrole-catalyzed oxidation of sulfides with iodobenzene diacetate

Manganese(IV) corroles catalyze efficient and selective sulfoxidations with iodobenzene diacetate as the mild oxygen source. The mechanistic studies suggested the different active oxidant forms were involved and significantly affected the catalytic activity. [Display omitted] •Manganese corroles cat...

Full description

Saved in:
Bibliographic Details
Published in:Inorganica Chimica Acta 2019-03, Vol.487, p.41-49
Main Authors: Ranburger, Davis, Willis, Ben, Kash, Benjamin, Jeddi, Haleh, Alcantar, Christian, Zhang, Rui
Format: Article
Language:English
Subjects:
Active control
Catalysis
Catalytic activity
Iodobenzene diacetate
Manganese
Manganese corrole
Organic chemistry
Oxidation
Substrates
Sulfide
Sulfides
Sulfoxide
Sulfoxides
Valence
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Manganese(IV) corroles catalyze efficient and selective sulfoxidations with iodobenzene diacetate as the mild oxygen source. The mechanistic studies suggested the different active oxidant forms were involved and significantly affected the catalytic activity. [Display omitted] •Manganese corroles catalyzed efficient sulfoxidations with iodobenzene diacetate.•The reaction conditions, substrate scope and catalyst effects were investigated.•The synthetic utility of this catalytic method was demonstrated.•Kinetic and competition studies were conducted to probe the active oxidants. Manganese corrole complexes catalyze the efficient oxidation of organic sulfides to sulfoxides with iodobenzene diacetate [PhI(OAc)2] as a mild oxygen source in the presence of small amounts of water. Various substituted thioanisoles can be efficiently oxidized to sulfoxides with quantitative conversions (up to 2500 TONs) and excellent selectivies for sulfoxides. The catalyst effects, including the corrole ligands and oxidation states of the central manganese, were investigated, and showed a significant impact on the catalytic sulfoxidations. The previously known high-valent manganese(V)-oxo corroles were chemically generated and kinetically studied in the oxidation of thioanisole substrates. The competition results suggested the oxidation state of manganese metal is crucial to control the nature of active oxidant forms that significantly affected their catalytic activity.
ISSN:0020-1693
1873-3255
DOI:10.1016/j.ica.2018.11.048