Spectroscopic, Structural, and Mass Spectrometric Studies on Two Systematic Series of Dithiabismuth(III) Heterocycles: Identification of Bismuthenium Cations and Their Solvent Complexes

General, high-yield metathesis reactions provide two related and
comprehensive series of dithiabismuth
heterocycles. The compounds are characterized by spectroscopic and
X-ray crystallographic analysis. Monocycles
2-chloro-1,3-dithia-2-bismolane (1),
2-chloro-1,3-dithia-2-bismane (2),
2-chloro-1,3-dithia-2-bismepane (3), 2-chloro-1,3,6-trithia-2-bismocane (4), and
2-chloro-1,3-dithia-6-oxa-2-bismocane (5) are kinetically
stable with respect to
the tethered bicyclic derivatives
1,2-bis((1,3-dithia-2-bismolan-2-yl)thio)ethane
(6), 1,3-bis((1,3-dithia-2-bisman-2-yl)thio)propane (7),
1,4-bis((1,3-dithia-2-bismepan-2-yl)thio)butane
(8),
bis((1,3,6-trithia-2-bismocan-2-yl)thio)ethyl)
sulfide (9), and
bis(((1,3-dithia-6-oxa-2-bismocan-2-yl)thio)ethyl) ether
(10). Mass spectrometry provides an
excellent
means of characterization of compounds of this nature and is
responsible for the identification of monocyclic
bismuthenium cations as general and dominant dissociation products.
In addition, the atmospheric pressure chemical
ionization technique reveals solvent coordination chemistry of the
bismuthenium cations.