Trisulfur Research Articles

ChemInform Abstract: Trisulfur Radical Anion as the Key Intermediate for the Synthesis of Thiophene via the Interaction Between Elemental Sulfur and NaOtBu.

A facile base-promoted sulfur-centered radical generation mode and a single-step protocol for the synthesis of thiophene derivatives using 1,3-diynes via the interaction between elemental sulfur and NaOtBu has been reported. EPR experiments revealed that the trisulfur radical anion acts as a key intermediate of this process. A plausible mechanism has been proposed.

Trisulfur radical anion as the key intermediate for the synthesis of thiophene via the interaction between elemental sulfur and NaOtBu.

A facile base-promoted sulfur-centered radical generation mode and a single-step protocol for the synthesis of thiophene derivatives using 1,3-diynes via the interaction between elemental sulfur and NaOtBu has been reported. EPR experiments revealed that the trisulfur radical anion acts as a key intermediate of this process. A plausible mechanism has been proposed.

Lithium Complexes of Asymmetric Hydrogen Tetraimido Sulfate

Two novel monolithiated complexes, [(thf)2Li(NtBu)2(NHtBu)S(Ndipp)] (3) and [(thf)2Li(NtBu)2(NHtBu)S(Ndmp)] (4), are presented from the reaction of the neutral tri(tert-butyl)sulfur triimide S(NtBu)3 (1), nBuLi, and diisopropylaniline and dimethylaniline, respectively. These asymmetrically substituted hydrogen tetraimido sulfate complexes of lithium provide the opportunity to switch the metal in a transmetalation reaction and to introduce another substituent at the protonated imide function.

ChemInform Abstract: Ubiquitous Trisulfur Radical Anion: Fundamentals and Applications in Materials Science, Electrochemistry, Analytical Chemistry and Geochemistry

AbstractReview: 50 refs.

Ubiquitous trisulfur radical anion: fundamentals and applications in materials science, electrochemistry, analytical chemistry and geochemistry

The trisulfur radical anion [S3]˙(-) is well-known from inorganic chemistry textbooks as the blue chromophore in ultramarine blues in which this highly reactive species is trapped in a zeolitic framework. Recent findings have revealed that [S3]˙(-) has a multi-faceted role in a variety of media, including alkali metal-sulfur batteries, aqueous solutions at high temperatures and pressures, and ionic liquids; it has also been used to detect trace amounts of water in organic solvents. This tutorial review illustrates how various physical techniques are used to identify a reactive species in solution and shows how elucidation of electronic structures can be used to explain spectroscopic and structural properties. Examples of the function of [S3]˙(-) in materials science, electrochemistry, analytical chemistry and geochemistry are used to illustrate the widespread influence of this fundamentally important triatomic sulfur species.

Encapsulation and convex‐face thiozonolysis of triatomic sulfur (S3) with carbon nanotubes

Nanotubes are a class of host cavities increasingly used to encapsulate unstable molecules, yet none have been exploited to host reactive sulfur species, such as thiozone (S(3)). In this paper, density functional theory and (ONIOM) calculations were used to compute single-walled carbon nanotube (SWNT)-thiozone combinations for the inclusion of S(3) into the hollow nanotube space and to rationalize when 1,2,3-thiozonide formation can take place. Nanotube diameter selectivity for the isomerization of the C(2v) form of S(3) to the D(3h) form proved to be elusive. Acyclic C(2v) S(3) was ~6 kcal/mol more stable than cyclic D(3h) S(3) whether it was free or encapsulated within an SWNT. 1,2,3-Thiozonide formation took place on the convex side of nanotubes of low tube radii, such as the armchair (4,4) and (5,5) SWNTs. In terms of the reaction mode of C(2v) S(3), the 1,3-dipolar addition reaction was preferred compared with the [2 + 2] cycloaddition and chelotrope paths.

On the origin of cytotoxicity of the natural product varacin. A novel example of a pentathiepin reaction that provides evidence for a triatomic sulfur intermediate.

A density functional theoretical study is presented, which implicates a novel S(3)-cleavage in the decomposition of a pentathiepin. This study predicts an interconversion between a pentathiepin and an open-chain polysulfur ion intermediate from which a key determinant in the chemistry then follows. Expulsion of diatomic sulfur, S(2), is unlikely from the unimolecular collapse of the open-chain polysulfur ion. Instead, S(3) can dissociate due to an unusually long and weak sulfur-sulfur (S4-S5) bond. A mechanistic picture now emerges which predicts that the novel S-S cleavage reaction and the unanticipated S(3) fragmentation are a result of delocalization of the negative charge within the remaining carbon-sulfur fragment. The computed results presented here reveal a new aspect to the chemistry of pentathiepins, that of S(3) unit transfer, which is proposed to have significance in the mechanism of cytotoxicity of the natural product varacin, 1.

Matrix photochemistry of syn-(chlorocarbonyl)sulfenyl bromide, syn-ClC(O)SBr: precursor to the novel species anti-ClC(O)SBr, syn-BrC(O)SCl, and BrSCl.

The vapor of (chlorocarbonyl)sulfenyl bromide, ClC(O)SBr, was isolated in solid Ar, Kr, N(2), and Ar doped with 5% CO at 15 K, and the matrix was subsequently irradiated with broad-band UV--visible light (200 < or = lambda < or = 800 nm), the changes being followed by reference to the IR spectrum of the matrix. The initial spectrum showed the vapor of ClC(O)SBr to consist of more than 99% of the syn form (with the C==O bond syn with respect to the S--Br bond) in equilibrium with less than 1% of the anti conformer. Irradiation caused various changes to occur. First, conformational randomization took place, leading to a roughly equimolar mixture of the two rotamers, and so affording the first spectroscopic characterization of an anti-ClC(O)S-containing compound. Simultaneously, the novel constitutional isomer syn-BrC(O)SCl was also formed. Continued photolysis resulted in the decay of all these species while revealing a third reaction channel, leading to the elimination of CO and the formation of the new triatomic sulfur halide BrSCl. The assignment of the IR bands to the different products was made on the basis of the usual criteria, taking account (i) of the effects of the naturally occurring isotopic pairs (35)Cl/(37)Cl and (79)Br/(81)Br, (ii) of the vibrational properties of related molecules, and (iii) of the properties predicted for the relevant molecules by quantum chemical calculations.

Open (C2v) and closed (D3h) forms of the S3 molecule, thiozone

Ab initio molecular electronic structure theory has been used to predict the structures and relative energies of the normal and ring isomers of triatomic sulfur. Self-consistent-field theory was used in conjunction with a double zeta basis set S(11s7p/6s4p), augmented by three sets of s and p bond functions. After correction for the effects of electron correlation, the open and closed isomers of S3 are predicted to be nearly comparable energetically, the open form lying lower by 4.3 kcal.

Characterization of the trisulfur radical anion S3- in blue solutions of alkali polysulfides in hexamethylphosphoramide

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCharacterization of the trisulfur radical anion S3- in blue solutions of alkali polysulfides in hexamethylphosphoramideT. Chivers and I. DrummondCite this: Inorg. Chem. 1972, 11, 10, 2525–2527Publication Date (Print):October 1, 1972Publication History Published online1 May 2002Published inissue 1 October 1972https://doi.org/10.1021/ic50116a047RIGHTS & PERMISSIONSArticle Views847Altmetric-Citations94LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (384 KB) Get e-Alerts Get e-Alerts

The System Trisulfur Dichloride and Methylamine. The Preparation of N,N'-Dimethylcyclohexasulfur- 1,5-diimide

The System Trisulfur Dichloride and Methylamine. The Preparation of N,N'-Dimethylcyclohexasulfur- 1,5-diimide