ELECTRONIC STRUCTURES OF TETRAHEDRAL COBALT(II) COMPLEXES
ELECTRONIC STRUCTURES OF TETRAHEDRAL COBALT(II) COMPLEXES
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DOI：
10.1021/ja01484a002
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发表时间：
1961-01-01
影响因子：
15
通讯作者：
GOODGAME, DM
中科院分区：
文献类型：
--
作者：
COTTON, FA;GOODGAME, M;GOODGAME, DM
本文报道了Co(II)四面体[CoI4]2-，[CoBr4]2-，[CoCH]2-的光谱和磁学性质。还给出了一些其他四面体物种的新数据，并从这些数据和以前报道的数据中得出了以下关于四面体Co(II)配合物及其电子结构的一般性结论：(1)根据这些值推导出的光谱化学系列中的配体的顺序与已建立的顺序很好地一致，并且现在几个额外的配体准确地或近似地位于一般顺序中。(2)从racah参数(B‘)和自旋-轨道耦合常数(’)，我们得到了两条或多或少独立的证据，表明在这些配合物中存在明显的金属和配体轨道的重叠。(3)[CoX4]2-离子在Co(II)的水溶液中可能没有或只有部分获得，即使在饱和的HX或LiX(X=Cl，Br，I)时也是如此。(4)Co(OH)2溶解在浓碱金属氢氧化物中得到一个或多个四面体物种，可能是[Co(OH)4]2“和/或[Co(OH)3(H20)]-。
Thorough spectral and magnetic studies of the tetrahedral Co (II) species [CoI4] 2-,[CoBr4] 2-,[CoCh] 2-, are reported. New data on some other tetrahedral species are also given, and from these and previously reported data the following general conclusions, inter alia, about tetrahedral Co (II) complexes and their electronic structures are drawn.(1) The order of ligands in the spectrochemical series, as deduced from the values, agrees well with the established order and several additional ligands are now accurately or approximately located in the general order.(2) From the Racah parameters (B'), and from the spin-orbit coupling constants ('), we obtain two more or less independent lines of evidence that appreciable overlap of metal and ligand orbitals occurs in these complexes.(3)[CoX4] 2-ions probably are not obtained, or only partially obtained, in aqueous solutions of Co (II), even when saturated with HX or LiX (X= Cl, Br, I).(4) Co (OH) 2 dissolves in concentratedalkali metal hydroxide to give one or more tetrahedral species, which probably are[Co (OH) 4] 2” and/or [Co (OH) 3 (H20)]-.