Coordination-Position Isomeric MIICuII and CuIIMII (M = Co, Ni, Zn) Complexes Derived from Macrocyclic Compartmental Ligands
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- 作者：Masami Yonemura ; Keisuke Arimura ; Koji Inoue ; Naoki Usuki ; Masaaki Ohba ; and Hisashi
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- 刊名：Inorganic Chemistry
- 出版年：2002
- 出版时间：February 11, 2002
- 年：2002
- 卷：41
- 期：3
- 页码：582 - 589
- 全文大小：122K
- 年卷期：v.41,no.3(February 11, 2002)
- ISSN：1520-510X
文摘
The dinucleating macrocyclic ligands (L2;2)2- and (L2;3)2-, comprised of two 2-[(N-methylamino)methyl]-6-(iminomethyl)-4-bromophenolate entities combined by the -(CH2)2- chain between the two aminic nitrogen atoms and by the-(CH2)2- or -(CH2)3- chain between the two iminic nitrogen atoms, have afforded the following MIICuII complexes:[CoCu(L2;2)](ClO4)2·MeCN (1A), [NiCu(L2;2)](ClO4)2 (2A), [ZnCu(L2;2)](ClO4)2·0.5MeCN·EtOH (3A), [CoCu(L2;3)(MeCN)(2-PrOH)](ClO4)2 (4A), [NiCu(L2;3)](ClO4)2 (5A), and [ZnCu(L2;3)](ClO4)2·1.5DMF (6A). [CoCu(L2;2)(MeCN)3](ClO4)2(1A') crystallizes in the monoclinic space group P21/n, a = 11.691(2) Å, b = 18.572(3) Å, c = 17.058(3) Å, 
=91.18(2)
, V = 3703(1) Å3, and Z = 4. [NiCu(L2;2)(DMF)2](ClO4)2 (2A') crystallizes in the triclinic space group P
,a = 11.260(2) Å, b = 16.359(6) Å, c = 10.853(4) Å, 
= 96.98(3), = 91.18(2), 
= 75.20(2), V = 1917(1)Å3, and Z = 2. 4A crystallizes in the monoclinic space group P21/c, a = 15.064(8) Å, b = 11.434(5) Å, c =21.352(5) Å, = 95.83(2), V = 3659(2) Å3, and Z = 4. The X-ray crystallographic results demonstrate the MIIto reside in the N(amine)2O2 site and the CuII in the N(imine)2O2 site. The complexes 1-6 are regarded to beisomeric with [CuCo(L2;2))](ClO4)2·DMF (1B), [CuNi(L2;2))](ClO4)2·DMF·MeOH (2B), [CuZn(L2;2))](ClO4)2·H2O (3B)),[CuCo(L2;3))](ClO4)2·2H2O (4B), [CuNi(L2;3))](ClO4)2 (5B), and [CuZn(L2;3))](ClO4)2·H2O (6B) reported previously,when we ignore exogenous donating and solvating molecules. The isomeric MIICuII and CuIIMII complexes aredifferentiated by X-ray structural, magnetic, visible spectroscopic, and electrochemical studies. The two isomericforms are significantly stabilized by the "macrocyclic effect" of the ligands, but 1A is converted into 1B on anelectrode, and 2A is converted into 2B at elevated temperature.
=91.18(2), V = 3703(1) Å3, and Z = 4. [NiCu(L2;2)(DMF)2](ClO4)2 (2A') crystallizes in the triclinic space group P,a = 11.260(2) Å, b = 16.359(6) Å, c = 10.853(4) Å, = 96.98(3), = 91.18(2), = 75.20(2), V = 1917(1)Å3, and Z = 2. 4A crystallizes in the monoclinic space group P21/c, a = 15.064(8) Å, b = 11.434(5) Å, c =21.352(5) Å, = 95.83(2), V = 3659(2) Å3, and Z = 4. The X-ray crystallographic results demonstrate the MIIto reside in the N(amine)2O2 site and the CuII in the N(imine)2O2 site. The complexes 1-6 are regarded to beisomeric with [CuCo(L2;2))](ClO4)2·DMF (1B), [CuNi(L2;2))](ClO4)2·DMF·MeOH (2B), [CuZn(L2;2))](ClO4)2·H2O (3B)),[CuCo(L2;3))](ClO4)2·2H2O (4B), [CuNi(L2;3))](ClO4)2 (5B), and [CuZn(L2;3))](ClO4)2·H2O (6B) reported previously,when we ignore exogenous donating and solvating molecules. The isomeric MIICuII and CuIIMII complexes aredifferentiated by X-ray structural, magnetic, visible spectroscopic, and electrochemical studies. The two isomericforms are significantly stabilized by the "macrocyclic effect" of the ligands, but 1A is converted into 1B on anelectrode, and 2A is converted into 2B at elevated temperature.