高等学校化学学报 ›› 1991, Vol. 12 ›› Issue (12): 1659.

• 研究论文 • 上一篇    下一篇

系列Fe4S4簇合物的光谱分析

牛淑云, 李淑琴, 南玉明, 徐吉庆, 蔡辉, 王铁钢   

  1. 吉林大学化学系, 长春, 130023
  • 收稿日期:1990-08-29 出版日期:1991-12-24 发布日期:1991-12-24
  • 通讯作者: 牛淑云
  • 基金资助:

    国家自然科学基金

Spectroscopic Analysis of a Series of Fe4S4Clusters

Niu Shu-yun, Li Shu-qin, Nan Yu-ming, Xu Ji-qing, Cai Hui, Wang Tie-gang   

  1. Department of Chemistry, Jilin University, Changchun, 130023
  • Received:1990-08-29 Online:1991-12-24 Published:1991-12-24

摘要: 本文报道了自合成的4种类立方烷型Fe4S4簇合物[Et4N][Fe4S4(Et2dtc)4]、[Et4N]2·[Fe4S4(Et2dtc)4]、[Et4N]3[Fe4S4(Et2dtc)4]、[Bu4N]2[Fe4S4(PhS)4]的UV-Vis和IR光谱数据,对照X光衍射测定结果,依据配体场弱场理论,对各光谱进行了分析和指认。讨论了配离子构型、中心离子氧化态对d-d带和荷迁移带的影响及键长、配位环境等几何因素与振动带的关系。

关键词: Fe4S4簇合物, 类立方烷型, 光谱分析和指认

Abstract: The data of electronic and infrared spectra are reported for the following four Fe4S4clusters: (Ⅰ) [Et4N][Fe4S4(Et2dtc)4], (Ⅱ) [Et4N],[Fe4S4(Et2dtc)4], (Ⅲ)[Et4N]3[Fe4S4(Et2dtc)4],(W)[Bu4N]2[Fe4S4(Ph-S)4]. According to the weak-ligand-field theory and the structure informations provided by X-ray diffraction, all the spectra were analyzed, assigned and listed in this paper. Comparing the individual spectra with each other, the following regulations can be drawn: (1) If the geometric structures of coordination anions are the same, the change of valence state of the central ion causes the apparent shifts of d-d bands in the electronic spectra and maintains infrared spectra principally. (2) In the coordination anions, the increase of oxidation state of the central ion results in the red-shift of M←L charge transfer bands. (3) If electron-pushing ability of the groups connected with the coordinating atom increases, the vibration bands of M-L bond move to the higher frequencies. These regulations above just show that our assignment to the spectra is reasonable.

Key words: Fe4S4cluster, Cubane-like, Analysis and assignment of spectra

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