Catalytic sulfoxidation and epoxidation with a Mn(III) triazacorrole: evidence for a "third oxidant" in high-valent porphyrinoid oxidations

Sheena Hailin Wang; Beaven S Mandimutsira; Ryan Todd; Bobby Ramdhanie; Joseph P Fox; David P Goldberg

doi:10.1021/ja038951a

Catalytic sulfoxidation and epoxidation with a Mn(III) triazacorrole: evidence for a "third oxidant" in high-valent porphyrinoid oxidations

J Am Chem Soc. 2004 Jan 14;126(1):18-9. doi: 10.1021/ja038951a.

Authors

Sheena Hailin Wang¹, Beaven S Mandimutsira, Ryan Todd, Bobby Ramdhanie, Joseph P Fox, David P Goldberg

Affiliation

¹ Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA.

PMID: 14709038
DOI: 10.1021/ja038951a

Abstract

The reaction between (TBP)8(Cz)Mn(III) (1) and the oxygen atom donors iodosylbenzene (PhIO) or p-cyanodimethylaniline-N-oxide (CDMANO) leads to the manganese(V)-oxo complex (TBP)8(Cz)Mn(V)O (2), which has been isolated and characterized previously. Under catalytic conditions with 1 as added catalyst and PhIO as oxidant, both sulfoxidation of PhSMe and epoxidation of cis-stilbene is observed, whereas with CDMANO no sulfoxidation takes place, suggesting that 2 is not the active oxidant. Examination of the independent reactivity of isolated 2 toward PhSMe and cis-stilbene supports this conclusion. A mechanism which relies on a novel type of oxidant involving Lewis acid activation of PhIO by the Mn(V)-oxo complex 2 accounts for these observations and is confirmed by 18O-labeling experiments.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Epoxy Compounds / chemical synthesis*
Manganese / chemistry*
Metalloporphyrins / chemistry*
Oxidation-Reduction
Oxygen Isotopes
Porphyrins / chemistry*
Sulfoxides / chemical synthesis*

Substances

Epoxy Compounds
Metalloporphyrins
Oxygen Isotopes
Porphyrins
Sulfoxides
corrole
Manganese