Abstract: A new and effective synthetic route for the high-yielding preparation of hexacyanometalates(III) (M = Ru, Os), which are valuable precursors of single-molecule and single-chain magnets, was investigated. A preparation procedure consisting in the heterogeneous oxidation of diamagnetic progenitors, K4[M(CN)6], increased the yield of the final product and permitted the number of complexes soluble in organic media to be substantially expanded owing to easier variation of the counterion. This synthetic approach was tested to obtain crystalline (cation)3[M(CN)6]·solvent products with organic cations such as n-tetrabutylammonium (nBu4N+), tetraethylammonium (Et4N+), bis(triphenylphosphine)iminium (PPN+), and tetraphenylphosphonium (Ph4P+). We also present the crystal and molecular structures of the two hexacyanometalates of Ru and Os, (Ph4P)3[M(CN)6]·solvent, by incorporating different solvate molecules, for which it was shown that the geometry of the metal coordination sphere is sensitive to both the bulkiness of the counterion and the nature of the solvate molecules. In the ruthenium compound, (Ph4P)3[Ru(CN)6]·2(iPrOH), some of CN groups are hydrogen bonded to 2-propanol, whereas in the osmium complex, (Ph4P)3[Os(CN)6]·3CH2Cl2·2H2O, the CN groups are bonded to water.

Cite: Samsonenko D.G. , Vostrikova K.E.
Effective Preparation of a Variety of Ruthenium and Osmium Cyanides: Valuable Precursors for Molecular Nanomagnets
European Journal of Inorganic Chemistry. 2016. V.2016. N9. P.1369-1375. DOI: 10.1002/ejic.201501354 WOS Scopus OpenAlex

Identifiers:

Web of science:	WOS:000373125700009
Scopus:	2-s2.0-84959432672
OpenAlex:	W2278502271

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DB	Citing
Scopus	5
OpenAlex	8
Web of science	3

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