Abstract
Joint thermolysis of the dinuclear pivalate complexes M2(μ-H2O)(μ-Piv)2(Piv)2(HPiv)4 (M = Co (1) and Ni (2), Piv- is the pivalate anion), in decane at 174 °C at the reactant ratio 1: 1 followed by treatment of the dry thermolysis product with methanol afforded crystals of a new cocrystallization product of the molecules containing the heterometallic cubane-like core M4(Co,Ni)O4. According to the X-ray diffraction data and the results of magnetic measurements, inductively coupled plasma atomic emission spectrometry (ICP-AES), and investigations of the solid-state thermal decomposition products, the isolated cocrystallization product has the general formula [Co1.6Ni2.4(μ3-OMe)4(μ2-Piv)2(pg2 -Piv)2(MeOH)4] ·4MeOH (3·4MeOH). Thermolysis of the crystals of the solvate 3·4MeOH is a destructive process accompanied by the intramolecular redox reaction. A mixture of metallic Ni and cobalt oxide (CoO) are the final solid decomposition products of 3 · 4MeOH in an argon atmosphere, whereas a mixture of the phases NiO, Co3O4, and NiCo2O4 is formed in air.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 685–691, April, 2010.
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Fomina, I.G., Dobrokhotova, Z.V., Aleksandrov, G.G. et al. Carboxylate clusters with the M4O4 cubane-like core: pivalate cocrystal containing CoII and NiII . Russ Chem Bull 59, 699–705 (2010). https://doi.org/10.1007/s11172-010-0149-5
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DOI: https://doi.org/10.1007/s11172-010-0149-5