衍生化二茂錳、二茂鐵和二茂鈷陰離子的分離與電子結構
作者：
小柯機器人發布時間：2020/12/19 14:05:40
英國曼徹斯特大學的David P. Mills課題組的一項最新研究成功實現了二茂錳、二茂鐵和二茂鈷陰離子的分離和電子結構測定。 相關論文於2020年12月14日發表於國際頂尖學術期刊《自然—化學》。
在該文中，課題組報導了作為3d金屬二茂化合物的同形家族——固態二茂鐵陰離子的分離，這類化合物是由金屬中心（錳，鐵或鈷）夾在兩個龐大的Cpttt配體之間（其中Cpttt是{1,2,4-C5H2tBu3}）形成的陰離子複合物。這些對熱和空氣敏感的複合物在高於30°C時迅速分解；但是，課題組研究人員還是能夠通過各種物理技術和從頭計算來表徵它們。這些數據也使得研究人員可以畫出這一類金屬二茂化合物的電子結構，其中包括一個19e-衍生化二茂鐵陰離子中意想不到的S=3/2高自旋基態。
據了解，二茂鐵在70年前被發現標誌著金屬二茂化合物的開端。雖然二茂鐵陽離子化合物在那之後很快就被發現了，但衍生化的二茂鐵二價陽離子在2016年才被分離出來，而二茂鐵的一價陰離子更是只在低溫電化學研究中被觀察到過。
附：英文原文
Title: Isolation and electronic structures of derivatized manganocene, ferrocene and cobaltocene anions
Author: Conrad A. P. Goodwin, Marcus J. Giansiracusa, Samuel M. Greer, Hannah M. Nicholas, Peter Evans, Michele Vonci, Stephen Hill, Nicholas F. Chilton, David P. Mills
Issue&Volume: 2020-12-14
Abstract: The discovery of ferrocene nearly 70 years ago marked the genesis of metallocene chemistry. Although the ferrocenium cation was discovered soon afterwards, a derivatized ferrocenium dication was only isolated in 2016 and the monoanion of ferrocene has only been observed in low-temperature electrochemical studies. Here we report the isolation of a derivatized ferrocene anion in the solid state as part of an isostructural family of 3d metallocenates, which consist of anionic complexes of a metal centre (manganese, iron or cobalt) sandwiched between two bulky Cpttt ligands (where Cpttt is {1,2,4-C5H2 tBu3}). These thermally and air-sensitive complexes decompose rapidly above 30°C; however, we were able to characterize all metallocenates by a wide range of physical techniques and ab initio calculations. These data have allowed us to map the electronic structures of this metallocenate family, including an unexpected high-spin S=3/2 ground state for the 19e derivatized ferrocene anion.
DOI: 10.1038/s41557-020-00595-w
Source: https://www.nature.com/articles/s41557-020-00595-w