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一种带有芳香π配体且含有最重第14族元素的二茂钌型配合物的合成与反应活性

Synthesis and reactivity of a ruthenocene-type complex bearing an aromatic π-ligand with the heaviest group 14 element.

作者信息

Nakada Marisa, Kuwabara Takuya, Furukawa Shunsuke, Hada Masahiko, Minoura Mao, Saito Masaichi

机构信息

Department of Chemistry , Graduate School of Science and Engineering , Saitama University , Shimo-okubo, Sakura-ku , Saitama-city , Saitama 338-8570 , Japan . Email:

Department of Chemistry , Graduate School of Science and Engineering , Tokyo Metropolitan University , 1-1 Minami-Osawa, Hachi-Oji , Tokyo , 192-0397 , Japan.

出版信息

Chem Sci. 2017 Apr 1;8(4):3092-3097. doi: 10.1039/c6sc04843a. Epub 2017 Feb 13.

Abstract

An anionic ruthenocene derived from a dilithioplumbole complex was prepared. In the complex, the plumbole ligand coordinates a ruthenium atom in an η-fashion, similar to the cyclopentadienyl ligand in ferrocene. The ruthenocene that has the aromatic π-ligand with the heaviest group 14 element reacted with electrophiles to afford the plumbole complexes wherein the plumbole ligands show deviation from planarity, in contrast to the planar plumbole ring in the anionic ruthenocene. The bent angles of the plumbole ligands are dependent on the substituents on the lead atoms. Cyclic voltammetry measurements revealed that the plumbole complexes are oxidized more easily than the corresponding stannole complexes.

摘要

制备了一种由二锂化铅杂戊搭烯配合物衍生的阴离子钌茂。在该配合物中,铅杂戊搭烯配体以η-方式配位一个钌原子,类似于二茂铁中的环戊二烯基配体。这种具有第14族最重元素的芳香π-配体的钌茂与亲电试剂反应,得到铅杂戊搭烯配合物,其中铅杂戊搭烯配体呈现出与阴离子钌茂中的平面铅杂戊搭烯环不同的非平面性。铅杂戊搭烯配体的弯曲角度取决于铅原子上的取代基。循环伏安法测量表明,铅杂戊搭烯配合物比相应的锡杂戊搭烯配合物更容易被氧化。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/346a/5412479/2291a02a3a5b/c6sc04843a-f1.jpg

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