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Issue 15, 2015
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Rapid degradation of cyclic peroxides by titanium and antimony chlorides

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Abstract

First responders face extraordinary risks when dealing with organic peroxides such as TATP due to the extreme sensitivity of this class of explosives, and to a lack of a robust chemical means of safe and rapid neutralisation. The Lewis acids TiCl4 and SbCl3 have been found to demonstrate a novel degradation mechanism, with TiCl4 degrading a model cyclic peroxide in minutes when used in a two-fold excess, or ∼3 hours at half equivalence. The products cannot re-form peroxide compounds as is the case with acid degradation, suggesting the two mechanisms are fundamentally different. The Lewis acids mediate a rearrangement reaction in the cyclic peroxide backbone leading to relatively innocuous products through deactivation of oxidising O. Sub-stoichiometric TiCl4 reactions highlight a secondary reaction pathway that also leads to some oxidative chlorination products, possibly mediated by an unconfirmed titanium-oxychloride species. SbCl3 was found to exhibit similar reactivity to TiCl4, although at a slower rate. A mechanism is proposed, consistent with the observations for both stoichiometric and sub-stoichiometric quantities of TiCl4.

Graphical abstract: Rapid degradation of cyclic peroxides by titanium and antimony chlorides

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Publication details

The article was received on 16 Jan 2015, accepted on 24 Feb 2015 and first published on 25 Feb 2015


Article type: Paper
DOI: 10.1039/C5DT00200A
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Citation: Dalton Trans., 2015,44, 6775-6783

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    Rapid degradation of cyclic peroxides by titanium and antimony chlorides

    M. S. Bali, D. Armitt, L. Wallace and A. I. Day, Dalton Trans., 2015, 44, 6775
    DOI: 10.1039/C5DT00200A

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