Spinnato Davide, Nöthling Nils, Leutzsch Markus, van Gastel Maurice, Wagner Lucas, Neese Frank, Cornella Josep
Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr, Germany.
Nat Chem. 2025 Feb;17(2):265-270. doi: 10.1038/s41557-024-01691-x. Epub 2025 Jan 6.
The chemistry of low-valent bismuth compounds has recently unlocked new concepts in catalysis and unique electronic structure fundamentals. In this work, we describe the synthesis and characterization of a highly reduced bismuth salt featuring a cationic core based on three contiguous Bi(I) centres. The triatomic bismuth-based core exhibits an electronic configuration that mimics the canonical description of the archetypical carbon-based π-allyl cation. Structural, spectroscopic and theoretical analyses validate the unique π-delocalization between the bismuth's highly diffused 6p orbitals, resulting in a bonding situation in which the three bismuth atoms are interconnected by two bonds, formally possessing a 1.5 bond order each. This electronic situation defines this complex as the heaviest and stable π-allyl cation of the periodic table. Furthermore, we demonstrate that the newly synthesized complex is able to act as a synthon for the transfer of a Bi(I) cation to forge other low-valent organobismuth complexes.
低价铋化合物的化学性质最近在催化和独特的电子结构基础方面开启了新的概念。在这项工作中，我们描述了一种高度还原的铋盐的合成与表征，该铋盐具有基于三个相邻Bi(I)中心的阳离子核心。基于铋的三原子核心呈现出一种电子构型，类似于典型的碳基π-烯丙基阳离子的经典描述。结构、光谱和理论分析证实了铋的高度离域6p轨道之间独特的π-离域，导致一种键合情况，其中三个铋原子通过两个键相互连接，形式上每个键的键级为1.5。这种电子情况将该配合物定义为元素周期表中最重且稳定的π-烯丙基阳离子。此外，我们证明新合成的配合物能够作为一种合成子，用于转移Bi(I)阳离子以形成其他低价有机铋配合物。
