The first oxygen-bridged diorganoarsenic(V) compound: the crystal structure of AsMe2(S)OAs(S)Me-2

L Silaghi-Dumitrescu, Sofia Pascu, I Silaghi-Dumitrescu, I Haiduc, M N Gibbons, D B Sowerby

Research output: Contribution to journalArticle

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Abstract

The oxidation of tetramethyldiarsinedisulfide, (AsMe2S)(2), with t-BuOOH under anhydrous conditions leads to both AsMe2(S)-S-As(O)Me-2 1 and AsMe2(S)-O-As(S)Me-2 2. The formation of the oxygen-bridged isomer 2 is unexpected and can he rationalised as resulting from either oxidation of the As(III)/As(III) form of the disulfide, (AsMe2-S-S-AsMe2), or by an oxotropic rearrangement of 1 via a cyclic As2OS transition state. RHF/3-21G* ab initio calculations predict that the ore-bridged species 2 is more stable than the thio-bridged form 1. The molecular structure of 2 has been determined by single crystal X-ray diffraction.
Original languageEnglish
Pages (from-to)187-192
Number of pages6
JournalJournal of Organometallic Chemistry
Volume549
Issue number1-2
DOIs
Publication statusPublished - 1997

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Molecular Structure
X-Ray Diffraction
Disulfides
Crystal structure
Oxygen
Oxidation
oxidation
crystal structure
disulfides
oxygen
Isomers
Molecular structure
Ores
molecular structure
isomers
minerals
Single crystals
X ray diffraction
single crystals
diffraction

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The first oxygen-bridged diorganoarsenic(V) compound: the crystal structure of AsMe2(S)OAs(S)Me-2. / Silaghi-Dumitrescu, L; Pascu, Sofia; Silaghi-Dumitrescu, I; Haiduc, I; Gibbons, M N; Sowerby, D B.

In: Journal of Organometallic Chemistry, Vol. 549, No. 1-2, 1997, p. 187-192.

Research output: Contribution to journalArticle

Silaghi-Dumitrescu, L, Pascu, S, Silaghi-Dumitrescu, I, Haiduc, I, Gibbons, MN & Sowerby, DB 1997, 'The first oxygen-bridged diorganoarsenic(V) compound: the crystal structure of AsMe2(S)OAs(S)Me-2', Journal of Organometallic Chemistry, vol. 549, no. 1-2, pp. 187-192. https://doi.org/10.1016/s0022-328x(97)00500-7
Silaghi-Dumitrescu, L ; Pascu, Sofia ; Silaghi-Dumitrescu, I ; Haiduc, I ; Gibbons, M N ; Sowerby, D B. / The first oxygen-bridged diorganoarsenic(V) compound: the crystal structure of AsMe2(S)OAs(S)Me-2. In: Journal of Organometallic Chemistry. 1997 ; Vol. 549, No. 1-2. pp. 187-192.
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AU - Silaghi-Dumitrescu, L

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AU - Haiduc, I

AU - Gibbons, M N

AU - Sowerby, D B

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AB - The oxidation of tetramethyldiarsinedisulfide, (AsMe2S)(2), with t-BuOOH under anhydrous conditions leads to both AsMe2(S)-S-As(O)Me-2 1 and AsMe2(S)-O-As(S)Me-2 2. The formation of the oxygen-bridged isomer 2 is unexpected and can he rationalised as resulting from either oxidation of the As(III)/As(III) form of the disulfide, (AsMe2-S-S-AsMe2), or by an oxotropic rearrangement of 1 via a cyclic As2OS transition state. RHF/3-21G* ab initio calculations predict that the ore-bridged species 2 is more stable than the thio-bridged form 1. The molecular structure of 2 has been determined by single crystal X-ray diffraction.

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