德国马克斯普朗克研究所Josep Cornella课题组在金属有机化学研究中取得进展。他们的最新研究提出了一种三金属铋(I)基烯丙基阳离子。2025年1月6日出版的《自然—化学》发表了这项成果。

据悉，低价铋化合物的化学研究，最近在催化和独特的电子结构基础方面开启了新概念。

在这项工作中，课题组描述了一种高度还原的铋盐的合成和表征，该盐具有基于三个连续Bi(I)中心的阳离子核。铋基三原子核的电子构型，模仿了典型碳基π-烯丙基阳离子的典型描述。结构、光谱和理论分析，验证了铋高度不同的6p轨道之间独特的π离域，导致三个铋原子通过两个键相互连接的情况，每个键的形式键级为1.5。这种电子状态定义了这个配合物，是元素周期表中最重和最稳定的π-烯丙基阳离子。

此外，课题组人员证明了，新合成的配合物能够作为Bi(I)阳离子转移的合成物，来形成其他低价有机铋配合物。

附：英文原文

Title: A trimetallic bismuth(I)-based allyl cation

Author: Spinnato, Davide, Nthling, Nils, Leutzsch, Markus, van Gastel, Maurice, Wagner, Lucas, Neese, Frank, Cornella, Josep

Issue&Volume: 2025-01-06

Abstract: 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.

DOI: 10.1038/s41557-024-01691-x

Source: https://www.nature.com/articles/s41557-024-01691-x