易于切换的二氮杂卟啉双钯钳形配合物的 18π-、19π-和 20π-共轭。
Easily Switchable 18π-, 19π-, and 20π-Conjugation of Diazaporphyrin Double-Pincer Bispalladium Complexes.
机构信息
Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, and Integrated Research Consortium on Chemical Science (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan.
Department of Applied Physics, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603, Japan.
出版信息
Angew Chem Int Ed Engl. 2023 Mar 13;62(12):e202300437. doi: 10.1002/anie.202300437. Epub 2023 Feb 14.
Ni 3,7,13,17-tetrapyridyl-5,15-diazaporphyrin serves as a double tridentate ligand to Pd ions to provide a pincer-type bispalladium complex. Electrochemical analysis revealed that the bispalladium complex shows excellent ability to accept electrons and reversible redox properties due to the coordination of the two cationic Pd centers to the meso-nitrogen atoms. We isolated and characterized one- and two-electron reduction species of the bispalladium complex. The 20π antiaromatic nature of the two-electron reduction species was confirmed by H NMR spectroscopy, UV/Vis-near-IR (NIR) absorption spectra, and density functional theory (DFT) calculations. X-ray diffraction revealed highly twisted structures for the bispalladium complexes regardless of the oxidation state.
镍 3,7,13,17-四吡啶基-5,15-二氮杂卟啉作为双三齿配体与 Pd 离子配位，提供钳式双钯配合物。电化学分析表明，由于两个阳离子 Pd 中心与中氮原子的配位，双钯配合物具有优异的电子接受能力和可逆的氧化还原性质。我们分离并表征了双钯配合物的单电子和双电子还原物种。通过 1 H NMR 光谱、紫外/可见-近红外（NIR）吸收光谱和密度泛函理论（DFT）计算证实了双电子还原物种的 20π 反芳香性质。X 射线衍射表明，无论氧化态如何，双钯配合物都具有高度扭曲的结构。
Zotero 插件