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Oxygen Versus Sulfur: Structure and Reactivity of Substituted Arsine Oxides and Arsine Sulfides
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
2012 (English)In: Journal of Computational Chemistry, ISSN 0192-8651, E-ISSN 1096-987X, Vol. 33, no 1, 112-117 p.Article in journal (Refereed) Published
Abstract [en]

Although arsenic in its inorganic forms is a well know toxic agent, biotransformations in the environment and in the human body can produce organoarsenic compounds that are generally of much lower toxicity. Foremost among these products is a range of dimethylated arsine oxides and their analogous sulfides, which are crucial to the arsenic detoxification process. We have investigated the formation and interconversion of substituted and unsubstituted arsenicals (R(2)(2)As(=Z)R(1), R(2) = CH(3), R(1) = CH(2)CH(2)OH, CH(2)COOH; Z = S or O) with density functional theory (DFT)/B3LYP. Formation of isomers including a cyclic hydrogen bonded conformer is observed for the ethanol and acetate derivatives. Furthermore, investigating the reaction of arsine oxide with hydrogen sulfide revealed the formation of arsine sulfide via pentacoordinated trigonal bipyramidal intermediates. A tetragonal pyramidal transition state was located enabling exchange of equatorial and axial positions in the trigonal bipyramidal species. The reaction was proven exothermic for all studied substituents (Delta E(rxn) -50 to -80 kJ/mol). This fundamental study shows that H(2)S easily leads to the formation of thioorganoarsenicals. Conversion of arsine sulfides into their corresponding arsine oxides is experimentally accomplished with hydrogen peroxide, which could also be rationalized by means of ab initio calculations showing high exothermicity (Delta E(rxn) ca. -550 kJ/mol). Reactions are considered at different levels of theory (i.e., DFT, second and fourth order Moller-Plesset (MP) perturbation theory) including two solvation models for DFT, which show good agreement for resulting geometries and reaction energies. Hence, the widely used B3LYP/6-31G** combination is a suitable method for the description of molecular organoarsenicals.

Place, publisher, year, edition, pages
2012. Vol. 33, no 1, 112-117 p.
Keyword [en]
arsenic, reaction mechanisms, ab initio calculations, chalcogens, main group elements
National Category
Natural Sciences
URN: urn:nbn:se:uu:diva-165595DOI: 10.1002/jcc.21950ISI: 000297852200014OAI: oai:DiVA.org:uu-165595DiVA: diva2:478184
Available from: 2012-01-16 Created: 2012-01-09 Last updated: 2012-03-13Bibliographically approved

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Orthaber, Andreas
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