π-BONDING IN INORGANIC COMPOUNDS: III. A MAGNETOCHEMICAL STUDY OF HEXAHALOOSMATES AND HEXACHLORORHENATE

1 June 1961

journal article
Published by Canadian Science Publishing in Canadian Journal of Chemistry

Vol. 39 (6) , 1284-1289
https://doi.org/10.1139/v61-162

Abstract

The anomalously small magnetic moments of osmium(IV) and rhenium(IV) in their hexahalo complexes are investigated by measurement of the magnetic susceptibilities of the mixed crystal systems, K₂OsCl₆/K₂PtCl₆, K₂OsBr₆/K₂PtBr₆, and K₂ReCl₆/K₂PtCl₆. It is shown that only at high dilution is the magnetic behavior of the systems that which is expected from theory; therefore, extensive superexchange through the overlap of d-orbitals on the central atom and orbitals on the ligands takes place in the pure substances and in the concentrated systems. Determination of the spin–orbit coupling constant for OsCl₆²⁻ provides a value in agreement with estimates based on spectra.

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