A New Method for the Synthesis of Heterospin Complexes

被引:10
作者
Ovcharenko, Victor [1 ]
Kuznetsova, Olga [1 ]
Fursova, Elena [1 ]
Romanenko, Galina [1 ]
Bogomyakov, Artem [1 ]
机构
[1] Russian Acad Sci, Siberian Branch, Int Tomog Ctr, Novosibirsk 630090, Russia
来源
CRYSTALS | 2015年 / 5卷 / 04期
基金
俄罗斯基础研究基金会; 俄罗斯科学基金会;
关键词
cobalt(II); nickel(II); nitronyl nitroxide; imino nitroxide; redox transformation; new synthetic approach; TRANSITION-METAL-COMPLEXES; MAGNETIC-PROPERTIES; CRYSTAL-STRUCTURE; NITRONYL NITROXIDES; REDUCED DERIVATIVES; IMINO NITROXIDES; CONTRAST AGENTS; RADICALS; COPPER(II); BATTERIES;
D O I
10.3390/cryst5040634
中图分类号
O7 [晶体学];
学科分类号
0702 ; 070205 ; 0703 ; 080501 ;
摘要
The interaction of binuclear Co(II) pivalate [Co-2(H2O)Piv(4)(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 [Co-5(Piv)(4)(L4L22)-L-1]. A nontrivial peculiarity of the complex is the presence of both the starting nitronyl nitroxide L-1 and its deoxygenated derivative imino nitroxide L-2 (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 [Co-3(Piv)(2)(L2L22)-L-1]. 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 [Ni-2(H2O)Piv(4)(HPiv)(4)], however, led to the formation of a heterospin complex [(Ni3LL22)-L-1(Piv)(3)(HPiv)(3)] also containing both nitronyl nitroxide and imino nitroxide.
引用
收藏
页码:634 / 649
页数:16
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