钌(III)配合物中赤道面吡啶基配体立体选择性取代的晶体学证据。
Crystallographic evidence for the stereoselective substitution of equatorial pyridyl ligands in ruthenium(III) complexes.
作者信息
Iwasaki Chihiro, Hishinuma Ken, Takase Tsugiko, Oyama Dai
机构信息
Graduate School of Science and Engineering, Fukushima University, 1 Kanayagawa, Fukushima 960-1296, Japan.
Department of Natural Sciences and Informatics, Fukushima University, 1 Kanayagawa, Fukushima 960-1296, Japan.
出版信息
Heliyon. 2023 Apr 5;9(4):e14876. doi: 10.1016/j.heliyon.2023.e14876. eCollection 2023 Apr.
Mononuclear Ru complexes catalyze dioxygen formation via water splitting; therefore, a detailed investigation into their water-oxidation process is necessary. In this study, we synthesized a series of Ru(III) complexes containing a dianionic tridentate ligand with three pyridine groups (one coordinated to Ru while the other two are "free") and investigated their substitution reactions in a water/acetonitrile mixture. Among the monodentate pyridyl ligands, the one at the equatorial position was crystallographically proven to be selectively substituted. Therefore, our results experimentally demonstrate the proposed coordination geometry for an intermediate during water oxidation over Ru complexes.
单核钌配合物通过水分解催化生成 dioxygen；因此，有必要对其水氧化过程进行详细研究。在本研究中，我们合成了一系列含有三吡啶基二阴离子三齿配体（一个与 Ru 配位，另外两个“游离”）的 Ru(III) 配合物，并研究了它们在水/乙腈混合物中的取代反应。在单齿吡啶基配体中，经晶体学证明赤道位置的配体被选择性取代。因此，我们的结果通过实验证明了 Ru 配合物水氧化过程中中间体的配位几何结构。
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