Herein, the synthesis and characterization of dicationic dichalcogenide compounds [(SIPr)E](2)(OTf)(2)(3a-E) (E = S, Se, Te) based on a saturated N-heterocyclic carbene (NHC), SIPr [SIPr = C{N(Dipp)CH2}(2), Dipp = 2,6-iPr(2)C(6)H(3)] are reported. Treatment of SIPr (1a) with elemental chalcogens affords the heavier ketone derivatives (SIPr)E (2a-E), which readily undergo oxidative E-E coupling reactions with triflic anhydride to yield the corresponding products3a-E. Compounds3a-Eare air-stable crystalline solids and were characterized by NMR and UV/Vis spectroscopy as well as by X-ray diffraction methods.