Article

On the Highest Oxidation States of Metal Elements in MO4 Molecules (M = Fe, Ru, Os, Hs, Sm, and Pu)

Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University, Beijing 100084, China
Inorg. Chem., 2016, 55 (9), pp 4616–4625
DOI: 10.1021/acs.inorgchem.6b00442
Publication Date (Web): April 13, 2016
Copyright © 2016 American Chemical Society

Synopsis

The highest oxidation numbers in stable MO4 molecules of group-8 are VIII for M = Ru, Os, Hs, but only VI for Fe, V for Pu, and III for Sm. The nonmonotonous variation of maximum valence over the periodic table correlates with the atomic core and valence orbital radii and energies.

Abstract

Abstract Image

Metal tetraoxygen molecules (MO4, M = Fe, Ru, Os, Hs, Sm, Pu) of all metal atoms M with eight valence electrons are theoretically studied using density functional and correlated wave function approaches. The heavier d-block elements Ru, Os, Hs are confirmed to form stable tetraoxides of Td symmetry in 1A1 electronic states with empty metal d0 valence shell and closed-shell O2– ligands, while the 3d-, 4f-, and 5f-elements Fe, Sm, and Pu prefer partial occupation of their valence shells and peroxide or superoxide ligands at lower symmetry structures with various spin couplings. The different geometric and electronic structures and chemical bonding types of the six iso-stoichiometric species are explained in terms of atomic orbital energies and orbital radii. The variations found here contribute to our general understanding of the periodic trends of oxidation states across the periodic table.

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b00442.

  • Detailed software references, ground state electronic configurations of the MO4 molecules, total energies Eq of free atomic cations Mq+ (PDF)

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Article Views: 586 Times
Received 22 February 2016
Published online 13 April 2016
Published in print 2 May 2016
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