Hypervalency in sulfur? ab initio and DFT studies of the structures of thiosulfate and related sulfur oxyanions

@article{Nishimoto2003HypervalencyIS,
  title={Hypervalency in sulfur? ab initio and DFT studies of the structures of thiosulfate and related sulfur oxyanions},
  author={Akiko Nishimoto and Daisy Y. Zhang},
  journal={Sulfur Letters},
  year={2003},
  volume={26},
  pages={171 - 180}
}
The structures of thiosulfate (S2O3 2−) and four other isovalent sulfur oxyanions, S m O n 2− have been investigated at the MP2, MP4, and B3LYP levels of theory, with 6−31+G* as the basis set. By comparing the bond lengths in the dianions with those in the doubly protonated molecules, H2S m O n , the sulfur–oxygen and sulfur–sulfur bond orders have been estimated, based on a valence bond theory model. The conventional Lewis structures, which represent the central S atom as forming six covalent… 

Thiosulfoxide (Sulfane) Sulfur: New Chemistry and New Regulatory Roles in Biology

This review examines the nature of thiosulfoxide (sulfane, S0) sulfur, the history of its regulatory role, its generation in biological systems, and its functions in cells.

Revisiting a Historical Concept by Using Quantum Crystallography: Are Phosphate, Sulfate and Perchlorate Anions Hypervalent?

Experimental information from the new field of quantum crystallography validate long-known facts, or refute long-standing misunderstandings on hypervalent atoms in molecules.

Understanding the ring-opening, chelation and non-chelation reactions between nedaplatin and thiosulfate: a DFT study based on NBO, ETS-NOCV and QTAIM

Abstract The current work investigates a DFT-based in silico study on the mechanism of reaction between the anticancer drug nedaplatin [Pt(NH3)2(Gly-κ2O,O′)] (Gly = –OCCH2COO–) and the rescue agent

Dechlorination-Hydroxylation of Atrazine to Hydroxyatrazine with Thiosulfate: A Detoxification Strategy in Seconds.

It is reported that the addition of sodium thiosulfate can realize rapid hydroxylation of atrazine to hydroxyatrazine at pH ≤ 4 under room temperature and provides a nonoxidative strategy for atrazin detoxification in seconds.

Active site of the solvated thiosulfate ion characterized by hydration structures and dynamics.

The reactivity of the terminated sulfur atom within the thiosulfate ion (S2O3(2-)) when it is involved in chemical reactions was investigated through the properties of the molecular hydration shell,

References

SHOWING 1-10 OF 27 REFERENCES

On the role of d orbitals in sulfur hexafluoride

The role of d orbitals in the bonding of SF/sub 6/ is studied through natural population and natural hybrid orbital analysis of ab initio SCF wave functions. The sulfur d orbitals are found to

Bond Lengths and Bond Angles in Oxo, Hydroxo, and Alkoxo Molecules of Be, B, and C: A Close-Packed Nearly Ionic Model.

The experimental data are surveyed and it is suggested that the bond lengths and geometries of these molecules can be best understood in terms of a model in which anion-like ligands are close-packed around a cation-like central atom.

The Natural Bond Orbital Lewis Structure Concept for Molecules, Radicals, and Radical Ions

As the “Coulomb explosion”1 and other techniques add to our knowledge of molecular geometry, it is appropriate to recall the debt of gratitude that many theoretical concepts owe to structural

Rigorous interpretation of electronic wave functions. 2. Electronic structures of selected phosphorus, sulfur, and chlorine fluorides and oxides

Rigorous interpretive tools are used to analyze electronic wave functions of eight molecules and ions that are often believed to possess hypervalent electronic structures. The atomic charges,

Chemical bonding in hypervalent molecules. The dominance of ionic bonding and negative hyperconjugation over d-orbital participation

Does sulfur form six covalent bonds in CH{sub 3}SO{sub 2}Cl, F{sub 3}S{triple bond}N or carbon or phosphorus five bonds in F{sub 3}C=O{sup {minus}}, F{sub 3}P=O After a brief history of the

Chemistry of hypervalent compounds

Hypervalent Compounds (K. Akiba). Structure and Reactivity of Hypervalent Organic Compounds: General Aspects (K. Akiba). Characteristic Properties of Hypervalent Compounds: Static and Dynamic

THE NATURE OF THE CHEMICAL BOND. APPLICATION OF RESULTS OBTAINED FROM THE QUANTUM MECHANICS AND FROM A THEORY OF PARAMAGNETIC SUSCEPTIBILITY TO THE STRUCTURE OF MOLECULES

During the last four years the problem of the nature of the chemical bond has been attacked by theoretical physicists, especially Heitler and London, by the application of the quantum mechanics. This

Structural Inorganic Chemistry

One outcome of this mutual interaction between structure analysis and the older sciences has been the appearance of various monographs, and, to a lesser extent, the adoption of a new 'slant' in the treatment of old subjects in less specialized works.

The genetic basis of tetrathionate respiration in Salmonella typhimurium

The ttrRSBCA gene cluster confers on Escherichia coli the ability to respire with tetrathionate as electron acceptor and makes up a previously unrecognized class of molybdopterin‐dependent enzymes that carry out the reductive cleavage of sulphur–sulphur bonds.

The role of d functions in correlated wave functions : main group molecules

Large d function contributions to Hartree - Fock wave functions of sulfur - and phosphorus-containing molecules are often cited as evidence for hypervalent spd hybridization and for violations of the