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  New alkali metal osmium- and ruthenium hydrides

Bronger, W., Sommer, T., Auffermann, G., & Müller, P. (2002). New alkali metal osmium- and ruthenium hydrides. Journal of Alloys and Compounds, 330, 536-542. doi:10.1016/S0925-8388(01)01536-5.

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 Creators:
Bronger, W.1, Author              
Sommer, T., Author
Auffermann, G.2, Author              
Müller, P., Author
Affiliations:
1Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863404              
2Gudrun Auffermann, Inorganic Chemistry, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863432              

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Free keywords: metal hydrides; high pressure synthesis; crystal structure; neutron diffraction; magnetic properties
 Abstract: Previously unknown ternary metal hydrides A(x)OsH(z) and A(x)RuH(z) (A=alkali metal) were synthesized by the reaction of alkali metal hydrides with osmium or ruthenium under a hydrogen pressure up to 6000 bar. The crystal structures of the hydrides were determined using a combination of X-ray and neutron diffraction experiments with deuterated compounds on powdered samples. Na3OsH7 and Na3RuH7 crystallize at room temperature in a tetragonal structure type (space group: P4(2)/mnm), which is characterized by isolated [OsH7]- or [RuH7] anions. The coordination polyhedron formed by the seven hydrogen (deuterium) ligands can be described as a distorted pentagonal bipyramide. Magnetic susceptibility measurements on Na3OsH7 in the temperature range between 3.5 K and room temperature revealed a weak temperature independent paramagnetism. Quantum mechanical calculations confirm these facts and show in detail that the large value of the spin-orbit coupling constant is responsible for the magnetic behaviour of these compounds with the oxidation state +4 for the transition metal atoms. With the heavier alkali metals transition metal(IV) hydrides A(3- delta)OsH(7-delta) and A(3-delta)RuH(7-delta) could be synthesized. They crystallize with isotypic atomic arrangements related to the cryolite structure type. Highest hydrogen pressure during the reaction leads to the osmium(VI) hydrides Cs3OsH9 and Rb3OsH9. The atomic arrangement is characterized by [OsH8] polyhedra intercalated in a cubic HA(3) framework which corresponds to the ReO3 structure type. Within these polyhedra the hydrogen ligands occupy two 24-fold positions with a statistical distribution. (C) 2002 Elsevier Science BY All rights reserved.

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Language(s): eng - English
 Dates: 2002-01-17
 Publication Status: Published in print
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: eDoc: 16443
ISI: 000173087800110
DOI: 10.1016/S0925-8388(01)01536-5
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Title: Journal of Alloys and Compounds
  Alternative Title : J. Alloy. Compd.
Source Genre: Journal
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Publ. Info: -
Pages: - Volume / Issue: 330 Sequence Number: - Start / End Page: 536 - 542 Identifier: ISSN: 0925-8388