Oxidation of [Li-4\(NBut)(3)S\(2)]: a new route to sulfur triimides

Fleischer, R; Freitag, S; Stalke, D

Abstract

The oxidation reactions of [Li4{(NBut)3S}2] with oxygen and halogens (bromine and iodine) were investigated. In all these reactions a radical intermediate [Li3{(NBut)3S}2]˙ was observed, which was investigated by ESR spectroscopy. While the reaction with oxygen leads to the dianionic sulfur(VI) species [Li2(NBut)3SO], oxidation with halogens yields N,N ′,N ″-tris(tert-butyl)sulfur triimide S(NBut)3. The latter reaction provides an easy access to sulfur triimides. Some intermediates from the reaction of [Li4{(NBut)3S}2] with halogens could be isolated and characterised by X-ray structure analyses. The intermediates can be rationalised as adducts of a lithium halide and a monomeric [Li2(NBut)2S] unit to give [(thf )3Li3(µ3-X){(NBut)3S}] (X = Br or I). In the presence of oxygen the oxidation reaction of [Li4{(NBut)3S}2] with iodine affords an adduct of lithium iodide and the sulfate analogue [(thf )3Li3(µ3-I){(NBut)3SO}] is obtained. As revealed by X-ray structure analysis, this adduct is very similar to [(thf )3Li3(µ3-I){(NBut)3S}] in the solid state.

Citation

Fleischer, R., Freitag, S., & Stalke, D. (2018). Oxidation of [Li-4\(NBut)(3)S\(2)]: a new route to sulfur triimides. Dalton Transactions, 193-198. https://doi.org/10.1039/a707085c

• Journal Article Type: Article
• Publication Date: 2018
• Deposit Date: Sep 21, 2021
• Journal: Dalton Transactions
• Print ISSN: 1477-9226
• Electronic ISSN: 1477-9234
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Issue: 2
• Pages: 193-198
• DOI: https://doi.org/10.1039/a707085c
• Public URL: https://durham-repository.worktribe.com/output/1239917