Notes on bismuth

Bismuth triple-decker phthalocyanine: synthesis and structure

Jan Janczak a, Ryszard Kubiak b, Jens Richter c, Hartmut Fuess b

• https://www.sciencedirect.com/science/article/abs/pii/S0277538799001850

A trimetallic bismuth(I)-based allyl cation

• https://pmc.ncbi.nlm.nih.gov/articles/PMC11794141/

Davide Spinnato 1, Nils Nöthling 1, Markus Leutzsch 1, Maurice van Gastel 1, Lucas Wagner 1, Frank Neese 1,✉, Josep Cornella 1,✉
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PMCID: PMC11794141  PMID: 39762626
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.