Interfacial oxidation of decamethylferrocene by hexacyanoferrate: synthesis and characterization of [Fe-III(eta-C5Me5)(2)](3)[Fe-III(CN)(6)]center dot 2CH(2)Cl(2)center dot 6H(2)O

Decamethylferrocene in dichloromethane is readily oxidised by one equivalen t of aqueous hexacyanoferrate(III) by electron transfer at the liquid/liqui d interface. In the presence of excess hexacyanoferrate(III), the resulting [Fe-III(eta -C5Me5)(2)](+) ions are extracted into the organic phase, and upon addition of n-heptane, crystals of composition [Fe-III(eta -C5Me5)(2)] (3)[Fe-III(CN)(6)]. 2CH(2)Cl(2). 6H2O are formed. The structure has low sym metry and consists of a face-centred array of rows of staggered decamethylf errocenium ions, interspaced with negatively charged ribbons comprising hex acyanoferrate(III) ions and eclipsed decamethylferrocenium ions. Magnetic m easurements are consistent with a structure consisting of non-interacting l ow spin paramagnetic Fe-III centres. (C) 2001 Elsevier Science Ltd. All rig hts reserved.