Bismuth Atoms in Hydrocarbon Ligands: Bismepines as Rigid, Ditopic Arene Donors in Coordination Chemistry

Dibenzobismepines may be described as bismuth heterocycles containing two arene functional groups (see the graphic). The coordination chemistry of mono- and dinuclear bismepines has been investigated in solution and in the solid state, demonstrating that they can act as a new class of rigid, ditopic arene ligands. In contrast to the lighter N, P, and As homologues, the bismuth atom does not directly interact with the metal atom but influences the ligand properties through its energetically low lying 6s orbital, its low electronegativity, and its unusual bond lengths and angles. Analytical techniques applied in this work include (DOSY) NMR spectroscopy, single-crystal X-ray analysis, mass spectrometry, and DFT calculations.