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.