Arsenic halides reduction

The methyl arsenic system compromises two well-defined species, the pentamer (MeAs)5, a yellow pyrophoric oil (m.p. 12°C) and the purple black double-chain polymer, [(MeAs)2] (m.p. 204 °C). A red solid that is possibly the linear chain compound (MeAs) has also been described. The polymers are formed when samples of the pentamer are exposed to impurities like arsenic halides that are able to react with the arsenic-arsenic bond and may act as end groups. The most widely used method for the preparation of larger amounts of (MeAs)j is the reduction of methylarsonic acid, MeAsO(OH)2, or its sodium salt with hypophosphoric acid " °. Samples prepared by this method, however, may contain between 5 and 15% of impurities. A method that minimizes impurities is the reaction of MeAsHj with dibenzylmercury (equation 3) °. 

The induced reduction of chlorate can be inhibited by iodide, bromide and chloride ions. The effectiveness of these ions is about 400 10 1 in the given order. The order and the magnitude of the effect agree fairly well with the catalytic activity of these ions in the arsenic(III)-cerium(IV) reaction. This inhibition by halides is presumably connected with the opening of a new two-electron route for the arsenic(III)-cerium(IV) reaction. 

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