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Synthesis of homoleptic zirconium and hafnium dithiocarbamate 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(2-S2CNMeEt) (1), Zr(2-S2CNEt2)4 (2), and Hf(2-S2CNEt2)4 (4), a rare example of a crystal of a homoleptic hafnium CS2 inserted amide species, were characterized. A computational analysis confirmed 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.more » « less
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Turnley, Jonathan W.; Vincent, Kiruba Catherine; Pradhan, Apurva A.; Panicker, Isabel; Swope, Ryan; Uible, Madeleine C.; Bart, Suzanne C.; Agrawal, Rakesh (, Journal of the American Chemical Society)
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