Department of Chemistry, School of Natural Sciences, The University of Manchester, Manchester, UK.
Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM, USA.
Nat Chem. 2021 Mar;13(3):243-248. doi: 10.1038/s41557-020-00595-w. Epub 2020 Dec 14.
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 Cp ligands (where Cp is {1,2,4-CH Bu}). 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.
大约 70 年前，二茂铁的发现标志着茂金属化学的诞生。尽管随后很快就发现了二茂铁阳离子，但只有在 2016 年才分离出衍生化的二茂铁二阳离子，而二茂铁的单阴离子仅在低温电化学研究中观察到。在这里，我们报告了在固态中二茂铁阴离子的分离，作为包含一个金属中心（锰、铁或钴）的阴离子配合物的一部分，夹在两个庞大的 Cp 配体（Cp 是{1,2,4-CH Bu}）之间，这些配合物为阴离子，形成一个同构的 3d 茂金属家族。这些热和空气敏感的配合物在-30°C 以上迅速分解；然而，我们能够通过多种物理技术和从头算计算来表征所有的茂金属。这些数据使我们能够绘制出这个茂金属家族的电子结构，包括衍生化的二茂铁阴离子出人意料的高自旋 S = 3/2 基态。
