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Crystals 2015, 5(4), 634-649; doi:10.3390/cryst5040634

A New Method for the Synthesis of Heterospin Complexes

International Tomography Center, Siberian Branch of the Russian Academy of Sciences, Institutskаyа Str., 3а, Novosibirsk 630090, Russia
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Academic Editors: Martin T. Lemaire and Helmut Cölfen
Received: 21 September 2015 / Revised: 17 November 2015 / Accepted: 20 November 2015 / Published: 2 December 2015
(This article belongs to the Special Issue High Spin Molecules)
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Abstract

The interaction of binuclear Co(II) pivalate [Сo2(H2O)Piv4(HPiv)4] with nitronyl nitroxide HL1 (2-(2-hydroxy-5-nitrophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl) in organic solvents led to the formation of a pentanuclear heterospin complex [Co5(Piv)4L14L22]. A nontrivial peculiarity of the complex is the presence of both the starting nitronyl nitroxide L1 and its deoxygenated derivative imino nitroxide L2 (HL2: 2-(2-hydroxy-5-nitrophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-oxyl) in its coordination sphere. Based on this, a new synthetic approach was developed, which suggests the use of both the starting radical and the product of its reduction in the reaction with the metal. The suggested approach is a new method for the synthesis of heterospin compounds, including those that cannot be obtained by other methods. It was shown that the reaction of Co(II) pivalate with a mixture of HL1 and HL2 can give a trinuclear heterospin complex [Co3(Piv)2L12L22]. The replacement of Co(II) by Ni(II) completely suppresses the reduction of HL1 into HL2, and Ni(II) pivalate does not react with HL1. The use of a known mixture of HL1 and HL2 in the reaction with [Ni2(H2O)Piv4(HPiv)4], however, led to the formation of a heterospin complex [Ni3L1L22(Piv)3(HPiv)3] also containing both nitronyl nitroxide and imino nitroxide. View Full-Text
Keywords: cobalt(II); nickel(II); nitronyl nitroxide; imino nitroxide; redox transformation; new synthetic approach cobalt(II); nickel(II); nitronyl nitroxide; imino nitroxide; redox transformation; new synthetic approach
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MDPI and ACS Style

Ovcharenko, V.; Kuznetsova, O.; Fursova, E.; Romаnenko, G.; Bogomyakov, A. A New Method for the Synthesis of Heterospin Complexes. Crystals 2015, 5, 634-649.

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