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.
Revised: August 28, 2017 |
Published: July 11, 2017
Citation
Huang W., N. Jiang, W.E. Schwarz, P. Yang, and J. Li. 2017.Diversity of Chemical Bonding and Oxidation States in MS4 Molecules of Group 8 Elements.Chemistry - A European Journal 23, no. 44:10580-10589.PNNL-SA-126169.doi:10.1002/chem.201701117