Novel species for the sulfur zoo: isomers of S8

Wong, Ming Wah; Steudel, Yana; Steudel, Ralf

doi:10.1016/s0009-2614(02)01342-8

Cited by 51 publications

(55 citation statements)

References 30 publications

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“…These features are particularly important for the proper description of the sulfur-containing compounds examined in this work. [27,28,29] For instance, the geometries and stabilities of several cluster species are poorly predicted by the MP2 theory. [28] For the prism form of S 6 , we have previously shown that the MP2 theory grossly overestimates its stability owing to the lowlying unoccupied molecular orbitals.…”

Section: Methodsmentioning

confidence: 99%

“…[27,28,29] For instance, the geometries and stabilities of several cluster species are poorly predicted by the MP2 theory. [28] For the prism form of S 6 , we have previously shown that the MP2 theory grossly overestimates its stability owing to the lowlying unoccupied molecular orbitals. [29] As a consequence, the additivity approximation at the MP2 level is rather unsatisfactory.…”

Section: Methodsmentioning

confidence: 99%

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Electrophilic Attack on Sulfur–Sulfur Bonds: Coordination of Lithium Cations to Sulfur‐Rich Molecules Studied by Ab Initio MO Methods

Steudel

Wong

Steudel

2005

Chemistry A European J

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Complex formation between gaseous Li+ ions and sulfur-containing neutral ligands, such as H2S, Me2Sn (n = 1-5; Me = CH3) and various isomers of hexasulfur (S6), has been studied by ab initio MO calculations at the G3X(MP2) level of theory. Generally, the formation of LiS(n) heterocycles and clusters is preferred in these reactions. The binding energies of the cation in the 29 complexes investigated range from -88 kJ mol(-1) for [H2SLi]+ to -189 kJ mol(-1) for the most stable isomer of [Me2S5Li]+ which contains three-coordinate Li+. Of the various S6 ligands (chair, boat, prism, branched ring, and triplet chain structures), two isomeric complexes containing the S5==S ligand have the highest binding energies (-163+/-1 kJ mol(-1)). However, the global minimum structure of [LiS6]+ is of C(3v) symmetry with the six-membered S(6) homocycle in the well-known chair conformation and three Li--S bonds with a length of 256 pm (binding energy: -134 kJ mol(-1)). Relatively unstable isomers of S6 are stabilized by complex formation with Li+. The interaction between the cation and the S6 ligands is mainly attributed to ion-dipole attraction with a little charge transfer, except in cations containing the six sulfur atoms in the form of separated neutral S2, S3, or S4 units, as in [Li(S3)2]+ and [Li(S2)(S4)]+. In the two most stable isomers of the [LiS6]+ complexes, the number of S--S bonds is at maximum and the coordination number of Li+ is either 3 or 4. A topological analysis of all investigated complexes revealed that the Li--S bonds of lengths below 280 pm are characterized by a maximum electron-density path and closed-shell interaction.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Electrophilic Attack on Sulfur–Sulfur Bonds: Coordination of Lithium Cations to Sulfur‐Rich Molecules Studied by Ab Initio MO Methods

Steudel

Wong

Steudel

2005

Chemistry A European J

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“…A few additional electron density peaks still remain unexplained. The geometry of the S chains modeled into the electron density is compatible with that of sulfur species known from inorganic chemistry [see, for instance, the description of the structure of the S 8 ring in Rettig and Trotter (20), of the allotropic forms of elemental sulfur in Meyer (21), and of trivalent S atoms in Wong et al (22)]. The presence of a polysulfur chain is additionally supported by preliminary total X-ray fluorescence (TXRF) experiments, which resulted in an S content of SQR higher than expected from the protein sequence (S. Metz, C. Rittmeyer, B. Kolbesen, personal communication).…”

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confidence: 99%

The structure of Aquifex aeolicus sulfide:quinone oxidoreductase, a basis to understand sulfide detoxification and respiration

Marcia

Ermler

Peng

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

138

166

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Sulfide:quinone oxidoreductase (SQR) is a flavoprotein with homologues in all domains of life except plants. It plays a physiological role both in sulfide detoxification and in energy transduction. We isolated the protein from native membranes of the hyperthermophilic bacterium Aquifex aeolicus, and we determined its X-ray structure in the ''as-purified,'' substrate-bound, and inhibitorbound forms at resolutions of 2.3, 2.0, and 2.9 Å, respectively. The structure is composed of 2 Rossmann domains and 1 attachment domain, with an overall monomeric architecture typical of disulfide oxidoreductase flavoproteins. A. aeolicus SQR is a surprisingly trimeric, periplasmic integral monotopic membrane protein that inserts about 12 Å into the lipidic bilayer through an amphipathic helix-turn-helix tripodal motif. The quinone is located in a channel that extends from the si side of the FAD to the membrane. The quinone ring is sandwiched between the conserved amino acids Phe-385 and Ile-346, and it is possibly protonated upon reduction via Glu-318 and/or neighboring water molecules. Sulfide polymerization occurs on the re side of FAD, where the invariant Cys-156 and Cys-347 appear to be covalently bound to polysulfur fragments. The structure suggests that FAD is covalently linked to the polypeptide in an unusual way, via a disulfide bridge between the 8-methyl group and Cys-124. The applicability of this disulfide bridge for transferring electrons from sulfide to FAD, 2 mechanisms for sulfide polymerization and channeling of the substrate, S 2؊ , and of the product, Sn, in and out of the active site are discussed.flavoprotein ͉ monotopic membrane protein ͉ sulfide metabolism ͉ X-ray crystallography ͉ extremophilic organism

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“…In the original paper, [1] the ring opening energy for sulfur, S 8 , through the G3X(MP2) method [2] should have been cited. The author regrets that this work escaped his attention.…”

mentioning

confidence: 99%

The Variable Strength of the Sulfur–Sulfur Bond: 78 to 41 kcal – G3, CBS‐Q, and DFT Bond Energies of Sulfur (S₈) and Disulfanes XSSX (X = H, F, Cl, CH₃, CN, NH₂, OH, SH)

Denk

2009

Eur J Inorg Chem

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Novel species for the sulfur zoo: isomers of S8

Cited by 51 publications

References 30 publications

Electrophilic Attack on Sulfur–Sulfur Bonds: Coordination of Lithium Cations to Sulfur‐Rich Molecules Studied by Ab Initio MO Methods

Electrophilic Attack on Sulfur–Sulfur Bonds: Coordination of Lithium Cations to Sulfur‐Rich Molecules Studied by Ab Initio MO Methods

The structure of Aquifex aeolicus sulfide:quinone oxidoreductase, a basis to understand sulfide detoxification and respiration

The Variable Strength of the Sulfur–Sulfur Bond: 78 to 41 kcal – G3, CBS‐Q, and DFT Bond Energies of Sulfur (S₈) and Disulfanes XSSX (X = H, F, Cl, CH₃, CN, NH₂, OH, SH)

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Novel species for the sulfur zoo: isomers of S8

Cited by 51 publications

References 30 publications

Electrophilic Attack on Sulfur–Sulfur Bonds: Coordination of Lithium Cations to Sulfur‐Rich Molecules Studied by Ab Initio MO Methods

Electrophilic Attack on Sulfur–Sulfur Bonds: Coordination of Lithium Cations to Sulfur‐Rich Molecules Studied by Ab Initio MO Methods

The structure of Aquifex aeolicus sulfide:quinone oxidoreductase, a basis to understand sulfide detoxification and respiration

The Variable Strength of the Sulfur–Sulfur Bond: 78 to 41 kcal – G3, CBS‐Q, and DFT Bond Energies of Sulfur (S8) and Disulfanes XSSX (X = H, F, Cl, CH3, CN, NH2, OH, SH)

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The Variable Strength of the Sulfur–Sulfur Bond: 78 to 41 kcal – G3, CBS‐Q, and DFT Bond Energies of Sulfur (S₈) and Disulfanes XSSX (X = H, F, Cl, CH₃, CN, NH₂, OH, SH)