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.
The formation of salicylaldimine
derivatives via ring contraction
as byproducts in 2-aminotropone syntheses has been investigated. Salicylaldiminate
(SAI) complexes of the alkali metals Li–K have been synthesized
and transformed into heterobimetallic complexes. Important findings
include an unusual double heterocubane structure of the homometallic
sodium SAI, an unprecedented ligand-induced E/Z isomerization of the aldimine functional group in the
homometallic potassium SAI, and the first example of a structurally
authenticated mixed-metal SAI based on s-block central atoms. Rapid
equilibria have been shown to play a crucial role in the solution
phase chemistry of mixed-metal SAIs. Analytical techniques applied
in this work include (heteronuclear) NMR spectroscopy, VT- and DOSY
NMR spectroscopy, high-resolution mass spectrometry, single-crystal
X-ray diffraction analysis, and DFT calculations.
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