一种二钌邻二氧杂环戊烯配合物[Ru2(3,6-DTBDiox)4]-的结构和光谱表征，该配合物具有一个单占据分子轨道，其在整个分子上离域。

Structural and spectroscopic characterization of a diruthenium o-dioxolene complex possessing a singly occupied molecular orbital delocalized over the entire molecule, [Ru2(3,6-DTBDiox)4]-.

作者信息

Mochizuki Katsunori, Kawamura Takashi, Chang Ho-Chol, Kitagawa Susumu

机构信息

Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.

出版信息

Inorg Chem. 2006 May 15;45(10):3990-7. doi: 10.1021/ic052180p.

DOI:10.1021/ic052180p

PMID:16676959

Abstract

Chemical oxidation of [Ru2(6+)(3,6-DTBCat)4]2- affords [n-Bu4N][Ru2(3,6-DTBDiox)4].acetone (2.acetone). The oxidized species was characterized by X-ray crystallographic analysis and EPR, and the delocalization of the unpaired electron over the entire molecule was indicated. This example showed that the utilization of redox-active ligands into a Ru2 complex expanded the degree of freedom in the electronic structure. DFT calculations support this view, and the spin population was estimated to be approximately 18% and 82% for the Ru2 core and the four dioxolene ligands, respectively.

摘要

[Ru2(6+)(3,6 - DTBCat)4]2- 的化学氧化得到 [n - Bu4N][Ru2(3,6 - DTBDiox)4]·丙酮 (2·丙酮)。通过X射线晶体学分析和电子顺磁共振对氧化产物进行了表征，结果表明未成对电子在整个分子中发生了离域。该实例表明，将氧化还原活性配体引入Ru2配合物中扩展了电子结构的自由度。密度泛函理论计算支持这一观点，对于Ru2核心和四个二氧戊环配体，自旋布居分别估计约为18%和82%。