Syntheses of linear-type S-bridged trinuclear complexes composed of heavy d6 metal ions and 2-aminoethanethiolate:: comparative characterization by X-ray diffraction, spectroscopy and electrochemistry
Syntheses of linear-type S-bridged trinuclear complexes composed of heavy d6 metal ions and 2-aminoethanethiolate:: comparative characterization by X-ray diffraction, spectroscopy and electrochemistry
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DOI：
10.1016/s0020-1693(03)00490-0
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发表时间：
2004-01-09
影响因子：
2.8
通讯作者：
Okamoto, K
中科院分区：
文献类型：
--
作者：
Mahboob, N;Miyashita, Y;Okamoto, K
通过fac（S）-[M（aet）（3）]与RhCl（3）（.）3H（2）O.经SP-SephadexC-25柱层析分离得到内消旋（1a，2a）和外消旋（1b，2b）异构体。1b和2b通过柱色谱法进行光学拆分，并通过CD光谱进行表征。用X射线衍射法测定了1a、1b和2a的晶体结构，发现它们均为线型三核结构。中心Rh（111）离子具有d（6）电子构型，具有非简并的A型立方场项，并表现出长（RhM）-M-...距离、锐角S-M-S角和钝角Rh-S-M角。这与具有简并T型立方场项的配合物如[M ′ {M（aet）（3）}（2）]（n+）（M ′ = V-III，Mo-IV和Re-III，M = Ir-III，Rh-III，n = 3或4）相反。所有的异构体进行了比较，并在固态和溶液中的光谱化学和电化学性质进行了讨论。(C)2003 Elsevier B. V.保留所有权利。
The S-bridged trinuclear complexes composed of heavy d(6) metal ions, [Rh-III{M(aet)(3)}(2)](3+) (M = Ir-III(1), Rh-III(2); aet = 2-aminoethanethiolate), have been prepared by the reactions of fac(S)-[M(aet)(3)] with RhCl(3)(.)3H(2)O. The complexes were separated into meso (1a, 2a) and rac (1b, 2b) isomers by SP-Sephadex C-25 column chromatography. 1b and 2b were optically resolved by the column chromatographic method and characterized by CD spectroscopy. Crystal structures of la, 1b and 2a were determined by Xray diffraction, and it was found that they consist of linear-type trinuclear structures. The central Rh(111) ion in the present complexes has d(6) electronic configuration with the non-degenerated A-type cubic field term, and showed long (RhM)-M-... distances, acute S-M-S angles and obtuse Rh-S-M angles. These are in contrast with the complexes having the degenerated T-type cubic field term such as [M'{M(aet)(3)}(2)](n+) (M' = V-III, Mo-IV and Re-III, M = Ir-III, Rh-III, n = 3 or 4). All the isomers have been comparatively characterized and discussed in solid state and the solution for spectrochemical and electrochemical properties. (C) 2003 Elsevier B.V. All rights reserved.