Preparation and some properties of bis(trimethylenediamine)cobalt(III) complexes with a bidentate-N,S or -N,Se ligand.
Preparation and some properties of bis(trimethylenediamine)cobalt(III) complexes with a bidentate-N,S or -N,Se ligand.
复制标题
具有双齿-N,S 或-N,Se 配体的双(三亚甲基二胺)钴(III)配合物的制备和一些性质。
DOI：
10.1246/bcsj.58.1119
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发表时间：
1985
影响因子：
4
通讯作者：
J. Hidaka
中科院分区：
文献类型：
--
作者：
T. Konno;K. Okamoto;H. Einaga;J. Hidaka
首次合成了7个[Co（bidentate-N，S or -N，Se）（tn）2]型旋光钴（III）配合物，其中bidentate-N，S or -N，Se分别表示2-氨基乙硫基（aet），2-氨基乙硒基（aes），2-氨基乙亚磺酸基（aese），2-氨基乙亚磺酸基（aesi），2-（甲硫基）乙胺（mea）和2-（甲硒基）乙胺（mseea）.通过吸收光谱、圆二色谱和核磁共振氢谱对配合物进行了表征。所得配合物均为Λ构型。（+）550 CD在溶液中选择性地呈现Λ-（R）构型，而（+）550 CD在溶液中呈现Λ-（R）和Λ-（S）构型的混合物。与相应的双（乙二胺）钴（III）配合物的吸收光谱和CD光谱进行了讨论。Λ-（R）-和Λ-（S）-[Co（aese）（tn）2]2+异构体的CD光谱随时间变化，表明硫位差向异构化伴随着螯合环的外消旋化。
Seven optically active cobalt(III) complexes of [Co(bidentate-N,S or -N,Se)(tn)2] type were prepared for the first time; bidentate-N,S or -N,Se denotes 2-aminoethanethiolato (aet), 2-aminoethaneselenolato (aes), 2-aminoethanesulfenato (aese), 2-aminoethanesulfinato (aesi), 2-(methylthio)ethylamine (mea), and 2-(methyl-seleno)ethylamine (mseea). These complexes were characterized from their absorption, CD, and 1H NMR spectra. All complexes obtained were assigned to the Λ configuration. The (+)550CD mea isomer took selectively the Λ-(R) configuration in solution, while the (+)550CD mseea isomer a mixture of the Λ-(R) and Λ-(S) ones. The absorption and CD spectra of the complexes are discussed in comparison with those of the corresponding bis(ethylenediamine)cobalt(III) complexes. The Λ-(R)- and Λ-(S)-[Co(aese)(tn)2]2+ isomers showed the CD spectral change with time and it was suggested that the epimerization at sulfur was accompanied by the racemization of the skew pair of chelate rings.