SPECTROSCOPIC, STRUCTURAL, AND MASS-SPECTROMETRIC STUDIES ON 2 SYSTEMATIC SERIES OF DITHIABISMUTH(III) HETEROCYCLES - IDENTIFICATION OF BISMUTHENIUM CATIONS AND THEIR SOLVENT COMPLEXES

General, high-yield metathesis reactions provide two related and compr ehensive series of dithiabismuth heterocycles. The compounds are chara cterized by spectroscopic and X-ray crystallographic analysis. Monocyc les 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-bi smocane (4), and 2-chloro-1,3-dithia-6-oxa-2-bismocane (5) are kinetic ally stable with respect to the tethered bicyclic derivatives 1,2-bis( (1,3-dithia-2-bismolan-2-yl)thio (6), 1,3-bis((1,3-dithia-2-bisman-2-y l)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 spectr ometry provides an excellent means of characterization of compounds of this nature and is responsible for the identification of monocyclic b ismuthenium cations as general and dominant dissociation products. In addition, the atmospheric pressure chemical ionization technique revea ls solvent coordination chemistry of the bismuthenium cations.