英国曼彻斯特大学Liddle, Stephen T.团队报道了具有单极、双极和三极性共价键钍(iv) -锑配合物。相关研究成果发表在2024年2月20日出版的国际知名学术期刊《自然—化学》。

人们对金属-金属多重键合的兴趣不断增长，以进一步加深人们对元素周期表化学键合的理解。然而，尽管极性共价金属-金属多重键在d和p嵌段中是众所周知的，但在锕系元素中却相对不发达。在光谱或富勒烯受限物种中发现了同金属的例子，表现出极性共价σ键并辅以最多两个与格π键的异金属变体更为普遍。因此，在正常实验条件下确保极性共价锕系元素的双和三金属-金属键一直是一个重要目标。

该文中，研究人员利用母体锑化二氢阴离子的质子解耦和脱氢偶联化学，报道了一重、二重和三重的钍-锑键，从而在正常实验条件下，在元素周期表中一些最重的离子之间引入极性共价锕系元素-金属多重键，在锑中心几乎没有或根本没有庞大的取代基保护。这为重元素多重键合提供了基本的见解，特别是相对论体系中锕系元素的轨道能量驱动和重叠驱动共价之间的张力。

附：英文原文

Title: Thorium(iv)–antimony complexes exhibiting single, double, and triple polar covalent metal–metal bonds

Author: Du, Jingzhen, Dollberg, Kevin, Seed, John A., Wooles, Ashley J., von Hnisch, Carsten, Liddle, Stephen T.

Issue&Volume: 2024-02-20

Abstract: There is continued burgeoning interest in metal–metal multiple bonding to further our understanding of chemical bonding across the periodic table. However, although polar covalent metal–metal multiple bonding is well known for the d and p blocks, it is relatively underdeveloped for actinides. Homometallic examples are found in spectroscopic or fullerene-confined species, and heterometallic variants exhibiting a polar covalent σ bond supplemented by up to two dative π bonds are more prevalent. Hence, securing polar covalent actinide double and triple metal–metal bonds under normal experimental conditions has been a fundamental target. Here we exploit the protonolysis and dehydrocoupling chemistry of the parent dihydrogen-antimonide anion, to report one-, two- and three-fold thorium–antimony bonds, thus introducing polar covalent actinide–metal multiple bonding under normal experimental conditions between some of the heaviest ions in the periodic table with little or no bulky-substituent protection at the antimony centre. This provides fundamental insights into heavy element multiple bonding, in particular the tension between orbital-energy-driven and overlap-driven covalency for the actinides in a relativistic regime.

DOI: 10.1038/s41557-024-01448-6

Source: https://www.nature.com/articles/s41557-024-01448-6