| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1301827 | Inorganic Chemistry Communications | 2013 | 6 Pages |
•Novel polychalcogenides of the less-noble metals Mn, Fe, Zn are presented.•One pot synthesis by solvothermal reactions in liquid ammonia or methylamine.•Elemental sulfur and selenium are converted to polyanions of three to six atoms.•With methylamine, rarely known hexakis(methylamine)metal complexes are formed.
Solvothermal reactions of the less-noble metals Mn, Fe, and Zn with elemental sulfur or/and selenium in liquid ammonia or methylamine give a series of polyselenides and polysulfides, namely [Mn(NH3)6]Se3 (1), [Mn(MeNH2)6]Se4 (2), [Mn(NH3)6]S6 (3), [Fe(NH3)6]S6 (4), [Zn(NH3)6]S6 (5), [Mn(NH3)6]Se6 (6), [Fe(NH3)6]Se6 (7) and two mixed sulfideselenides [Mn(MeNH2)6](S5)0.15(S1.57Se2.43)0.85 (8) and [Mn(NH3)6](S2.71Se2.29) (9). All compounds represent ionic structures with octahedral [M(NH2R)6]2 + (M = Mn, Fe, Zn; R = H, CH3) complex cations and various polychalcogenide anions in the form of chains consisting of three to six sulfur and/or selenium atoms. The hexachalcogenides 4–7 are isostructural. In the structure of 8 S52 − and (S/Se)42 − anions are present in 15%: 85% ratio on one crystallographic site. 9 contains a (S/Se)52 − mixed chalcogenide anion. Generally, N–H∙∙∙S/Se bonding is weak, which facilitates the observed disorder of the polychalcogenide chains in the hexachalcogenides 4–7. The structures of 1–8 show a packing of cations and anions of the simple rock-salt structure type while 9 adopts the PtS structure type.
Graphical abstractSolvothermal reactions of the less-noble metals Mn, Fe, and Zn with elemental sulfur or/and selenium in liquid ammonia or methylamine give a series of polyselenides and polysulfides. All compounds represent ionic structures with octahedral [M(NH3)6]2 + and [M(NH2CH3)6]2 +complex cations (M = Mn, Fe, Zn) and various polychalcogenide anions in the form of chains consisting of three to six sulfur and/or selenium atoms.Figure optionsDownload full-size imageDownload as PowerPoint slide
