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Darstellung und Redoxverhalten aller bindungsisomeren Hexakis(thiocyanato(N)-thiocyanato(S))-osmate(III) und (IV), [Os(NCS)n(SCN)6-n]3-/2-, n = 0—6, einschließlich der Stereoisomeren / Preparation and Electrochemical Behaviour of All Bond-Isomeric Hexakis(thiocyanato(N)-thiocyanato(S))osmates(III) and (IV), [Os(NCS)n(SCN)6-n]3-/2-, n = 0—6, Including Stereoisomers

Darstellung und Redoxverhalten aller bindungsisomeren... AbstractThe first two complete series of all 10 possible linkage and geometric isomers of the general formula [Os(NCS)n(SCN)6-n]3-/2- have been obtained. The Os(III) complexes, some of which have been previously known, are prepared from the reactions of K2[OsX6], X = Cl. Br. I, and K2[OsO2(OH)4] with excess aqueous or methanolic KSCN solution and subsequent chromato­graphic separation on DEAE cellulose. Oxidation with Ce(IV) in acetone or methanol yields the corresponding Os(IV) compounds without changes in the ligand sphere except for n = 0, but pure salts of [Os(SCN)6]2“ are isolated by repeated recrystallization. S-bonding is less favoured in Os(IV) than in Os(III), proving that Os(IV) is the harder Lewis acid. Cyclic voltammograms of all isomers show two waves, a mainly irreversible Os(II)/Os(III) couple and a reversible Os(III)/Os(IV) couple. Characteristic shifts of the half-wave potentials of both electron transfer reactions within the series give strong evidence of π-back donation to -NCS. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Zeitschrift für Naturforschung B de Gruyter

Darstellung und Redoxverhalten aller bindungsisomeren Hexakis(thiocyanato(N)-thiocyanato(S))-osmate(III) und (IV), [Os(NCS)n(SCN)6-n]3-/2-, n = 0—6, einschließlich der Stereoisomeren / Preparation and Electrochemical Behaviour of All Bond-Isomeric Hexakis(thiocyanato(N)-thiocyanato(S))osmates(III) and (IV), [Os(NCS)n(SCN)6-n]3-/2-, n = 0—6, Including Stereoisomers

Bütje, K.; Preetz, W.
Zeitschrift für Naturforschung B , Volume 43 (4): 7 – Apr 1, 1988
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Publisher
de Gruyter
Copyright
© 1946 – 2014: Verlag der Zeitschrift für Naturforschung
ISSN
0932-0776
eISSN
1865-7117
DOI
10.1515/znb-1988-0402
Publisher site
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Abstract

AbstractThe first two complete series of all 10 possible linkage and geometric isomers of the general formula [Os(NCS)n(SCN)6-n]3-/2- have been obtained. The Os(III) complexes, some of which have been previously known, are prepared from the reactions of K2[OsX6], X = Cl. Br. I, and K2[OsO2(OH)4] with excess aqueous or methanolic KSCN solution and subsequent chromato­graphic separation on DEAE cellulose. Oxidation with Ce(IV) in acetone or methanol yields the corresponding Os(IV) compounds without changes in the ligand sphere except for n = 0, but pure salts of [Os(SCN)6]2“ are isolated by repeated recrystallization. S-bonding is less favoured in Os(IV) than in Os(III), proving that Os(IV) is the harder Lewis acid. Cyclic voltammograms of all isomers show two waves, a mainly irreversible Os(II)/Os(III) couple and a reversible Os(III)/Os(IV) couple. Characteristic shifts of the half-wave potentials of both electron transfer reactions within the series give strong evidence of π-back donation to -NCS.

Journal

Zeitschrift für Naturforschung B – de Gruyter

Published: Apr 1, 1988

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