Magnetic and spectroscopic characterizations of high-spin cobalt(II) complex with soft-scorpionate ligand
Magnetic and spectroscopic characterizations of high-spin cobalt(II) complex with soft-scorpionate ligand
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DOI：
10.1016/j.inoche.2012.01.003
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发表时间：
2012-03-01
影响因子：
3.8
通讯作者：
Nakano, Motohiro
中科院分区：
文献类型：
--
作者：
Baba, Haruyuki;Nakano, Motohiro
为了研究硫配体对金属配合物电子态的影响，采用一种分子上有三个硫配位的软蝎酸配体，制备了一种具有八面体[(CoS6)- s -II]核的新型高自旋钴（II）配合物[Co-II(Tbz)(2)] (Tbz（-) =氢（2-巯基苯并噻唑基）硼酸盐）。根据由两个d-d波段组成的配合物的电子能谱，估计配体场分裂和Racah参数分别为Delta(O)/hc = 8000 cm（-1）和B/hc = 560 cm（-1）。后者证明了由d-电子在配体上的离域引起的显着的非相干效应。这些参数被成功地用于磁化率的模拟。(C) 2012 Elsevier B.V.版权所有
For the purpose of investigating the effect of sulfur ligands on the metal complex electronic states, a soft scorpionate ligand, which bears three sulfur coordination sites on a molecule, was used to afford a novel high-spin cobalt(II) complex, [Co-II(Tbz)(2)] (Tbz(-) = hydrotris(2-mercaptobenzothiazolyl)borate), having an octahedral [(CoS6)-S-II] core. Based on the electronic spectrum of the complex consisting of two d-d bands, the ligand-field splitting and the Racah parameter were estimated as Delta(O)/hc = 8000 cm(-1) and B/hc = 560 cm(-1), respectively. The latter proved remarkable nephelauxetic effect arising from delocalization of d-electrons over the ligands. These parameters were successfully utilized in the simulation of the magnetic susceptibility. (C) 2012 Elsevier B.V. All rights reserved.