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Crystals 2015, 5(4), 634-649;

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
Author to whom correspondence should be addressed.
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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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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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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