Reductive Cleavage of Organic Peroxides by Iron Salts and Thiols

Authors

Anderw Olson, University of Nebraska - LincolnFollow
Abigail J. Jameson, University of Nebraska - Lincoln
Shiva K. Kyasa, Western New Mexico University
Boone W. Evans, University of Nebraska - LincolnFollow
Patrick H. Dussault, University of Nebraska-LincolnFollow

ORCID IDs

Shiva K. Kyasa

Patrick H. Dussault

Date of this Version

2018

Citation

ACS Omega 2018, 3, 14054−14063

Comments

© 2018 American Chemical Society

Open access

DOI: 10.1021/acsomega.8b01977

Abstract

Despite the low bond strength of the oxygen− oxygen bond, organic peroxides are often surprisingly resistant to cleavage by nucleophiles and reductants. As a result, achieving decomposition under mild conditions can be challenging. Herein, we explore the reactivity of a selection of peroxides toward thiolates, phenyl selenide, Fe(II) salts, and iron thiolates. Peroxides activated by conjugation, strain, or stereoelectronics are rapidly cleaved at room temperature by thiolate anions, phenylselenide, or Fe(II) salts. Under the same conditions, unhindered dialkyl peroxides are only marginally reactive; hindered peroxides, including triacetone triperoxide and diacetone diperoxide (DADP), are inert. In contrast, all but the most hindered of peroxides are rapidly (<1 min at concentrations down to ∼40 mM) cleaved by mixtures of thiols and iron salts. Our observations suggest the possible intermediacy of strongly reducing complexes that are readily regenerated in the presence of stoichiometric thiolate or hydride. In the case of DADP, an easily prepared explosive of significant societal concern, catalytic amounts of iron and thiol are capable of promoting rapid and complete disproportionation. The availability of inexpensive and readily available catalysts for the mild reductive degradation of all but the most hindered of peroxides could have significant applications for controlled remediation of explosives or unwanted radical initiators.