A New Method for the Synthesis of Heterospin Complexes

Crystals

Victor Ovcharenko¹  Olga Kuznetsova²  Elena Fursova²  Gаlinа Romаnenko²  Artem Bogomyakov²  Martin T. Lemaire² 

[1] International Tomography Center, Siberian Branch of the Russian Academy of Sciences, Institutskаyа Str., 3а, Novosibirsk 630090, Russia;

关键词: cobalt(II);    nickel(II);    nitronyl nitroxide;    imino nitroxide;    redox transformation;    new synthetic approach;   

DOI  :  10.3390/cryst5040634

来源: mdpi

【 摘 要 】

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.

【 授权许可】

CC BY   
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