MOSSBAUER SPECTRA OF SOME TRIS(N,N-DISUBSTITUTED DITHIOCARBAMATO)IRON(3) COMPOUNDS
MOSSBAUER SPECTRA OF SOME TRIS(N,N-DISUBSTITUTED DITHIOCARBAMATO)IRON(3) COMPOUNDS
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DOI：
10.1021/ic50074a017
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发表时间：
1969-01-01
影响因子：
4.6
通讯作者：
STRAUB, DK
中科院分区：
文献类型：
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作者：
EPSTEIN, LM;STRAUB, DK
铁（Ⅲ）的三N，N-二取代二硫代氨基甲酸配合物，由Delepine于1908年首次合成，[1]自Cambi和他的同事在一系列出版物[2-8]中报道了大量这类配合物的制备并讨论了它们的化学和物理性质，特别是非常特殊的磁性行为以来，一直是许多研究的主题。铁（III），八面体由来自三个双齿配体的六个硫原子配位（络合物在溶液中是单体），9· 10在热平衡中以低自旋（2 T2）和高自旋（6Ai）状态存在。[9· 11]在Fe（III）S6型配合物中，这些配合物的独特之处在于，对于大多数配合物，两个自旋态之间的能量分离在室温下非常小。三（N-单取代二硫代羰基-bamato）铁（III）化合物是典型的高自旋配合物，2· 7和类似的双齿硫配体带-1电荷，既可以生成高自旋（如（C2 H60）2 PS2-）12，也可以生成低自旋（RCS 2-，C2 H6 OCS 2-）7，13铁（III）.已经提出的证据表明，铁血红素蛋白氢氧化物也存在于两个自旋状态。图14高自旋（例如，® T2）和低自旋（例如，4At）之间的类似平衡
The tris N, N-disubstituted dithiocarbamate com-plexes of iron (III), first prepared by Delepine in 1908, 1 have been the subject of numerous investigations since Cambi and his coworkers, in a long series of publica-tions, 2-8 reported the preparation and discussed the chemical and physical properties, especially the very peculiar magnetic behavior, of a large number of these complexes. The iron (III), octahedrally coordinated by six sulfur atoms from the three bidentate ligands (the complexes are monomeric in solution), 9· 10 exists in both low-spin (2T2) and high-spin (6Ai) states in thermal equilibrium. 9· 11 It appears that these com-plexes, among those of the Fe (III) S6 type, are unique in that, for most of the complexes, the energy separation between the two spin states is very small at room temperature. The tris (N-monosubstituted dithiocar-bamato) iron (III) compounds are typical high-spin complexes, 2· 7 and similar bidentate sulfur ligands with—1 charge give either high-spin (eg,(C2H60) 2PS2-) 12 or low-spin (RCS2-, C2H6OCS2-) 7, 13iron (III). Evidence has been presented that ferrihemoproteinhydroxides also exist in two spin states. 14 Similar equilibria be-tween high-spin (eg,® T2) and low-spin (eg, 4At)