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Title: Diversity of Chemical Bonding and Oxidation States in MS 4 Molecules of Group 8 Elements

Abstract

The geometric and electronic ground-state structures of six MS 4 molecules (M = group-8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density-functional and correlated wave-function approaches. The MS 4 species are compared to analogous MO 4 species recently investi-gated (Inorg. Chem. 2016, 55: 4616). Metal oxidation state (MOS) of high value VIII appears in low- spin singlet Td geometric species (Os,Hs)S 4 and (Ru,Os,Hs)O 4, whereas low MOS=II appears in high- spin septet D 2d species Fe(S 2) 2 and (slightly excited) metastable Fe(O 2) 2. The ground states of all other molecules have intermediate MOS values, containing S 2-, S 2 2-, S2 1- (and resp. O 2--, O 1-, O 2 2-, O 2 1-) ligands, bonded by ionic, covalent and correlative contributions.

Authors:
 [1]; ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China
  2. Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Physical and Theoretical Chemistry, University of Siegen, Siegen 57068 Germany
  3. Theoretical Division, Los Alamos National Laboratory, Los Alamos New Mexico 87545 USA; Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland Washington 953002 USA
  4. Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084 P.R. China; Environmental Molecular Science Laboratory, Pacific Northwest National Laboratory, Richland Washington 953002 USA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1378013
Report Number(s):
PNNL-SA-126169
Journal ID: ISSN 0947-6539; 830403000
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry - A European Journal; Journal Volume: 23; Journal Issue: 44
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Group-8 metals; Tetra-sulfides; Tetra-oxides; Oxidation states; Quantum chemistry; Relativistic effects; Electron correlation; Transition-metal chalcogenide bonding

Citation Formats

Huang, Wei, Jiang, Ning, Schwarz, W. H. Eugen, Yang, Ping, and Li, Jun. Diversity of Chemical Bonding and Oxidation States in MS 4 Molecules of Group 8 Elements. United States: N. p., 2017. Web. doi:10.1002/chem.201701117.
Huang, Wei, Jiang, Ning, Schwarz, W. H. Eugen, Yang, Ping, & Li, Jun. Diversity of Chemical Bonding and Oxidation States in MS 4 Molecules of Group 8 Elements. United States. doi:10.1002/chem.201701117.
Huang, Wei, Jiang, Ning, Schwarz, W. H. Eugen, Yang, Ping, and Li, Jun. Tue . "Diversity of Chemical Bonding and Oxidation States in MS 4 Molecules of Group 8 Elements". United States. doi:10.1002/chem.201701117.
@article{osti_1378013,
title = {Diversity of Chemical Bonding and Oxidation States in MS 4 Molecules of Group 8 Elements},
author = {Huang, Wei and Jiang, Ning and Schwarz, W. H. Eugen and Yang, Ping and Li, Jun},
abstractNote = {The geometric and electronic ground-state structures of six MS4 molecules (M = group-8 metals Fe, Ru, Os, Hs, Sm, and Pu) have been studied by using quantum-chemical density-functional and correlated wave-function approaches. The MS4 species are compared to analogous MO4 species recently investi-gated (Inorg. Chem. 2016, 55: 4616). Metal oxidation state (MOS) of high value VIII appears in low- spin singlet Td geometric species (Os,Hs)S4 and (Ru,Os,Hs)O4, whereas low MOS=II appears in high- spin septet D2d species Fe(S2)2 and (slightly excited) metastable Fe(O2)2. The ground states of all other molecules have intermediate MOS values, containing S2-, S22-, S21- (and resp. O2--, O1-, O22-, O21-) ligands, bonded by ionic, covalent and correlative contributions.},
doi = {10.1002/chem.201701117},
journal = {Chemistry - A European Journal},
number = 44,
volume = 23,
place = {United States},
year = {Tue Jul 11 00:00:00 EDT 2017},
month = {Tue Jul 11 00:00:00 EDT 2017}
}