Formation of Homoleptic Zirconium and Hafnium Dithiocarbamates via Insertion of CS2: Breaking Bonds and Taking Names

Syntheses of homoleptic zirconium and hafnium dithiocarbamates via carbon disulfide insertion into zirconium and hafnium amides were investigated for their utility as soluble molecular precursors for chalcogenide perovskites and binary metal sulfides. Treating M(NEtR)4 (M = Zr, Hf and R = Me, Et) with CS2 resulted in quantitative yields of homoleptic Group IV dithiocarbamates. Zr(κ2-S2CNMeEt) (1), Zr(κ2-S2CNEt2)4 (2), and Hf(κ2-S2CNEt2)4 (4), a rare example of a crystal of a homoleptic hafnium CS2-inserted amide species, were characterized. Computational analysis confirmed the assignments for IR spectroscopy. To exemplify the utility of the Group IV dithiocarbamates, a solution-phase nanoparticle synthesis was performed to obtain ZrS3 via the thermal decomposition of Zr(S2CNMeEt)4.