Synthesis and characterization of [Yb(NH{sub 3}){sub 8}][Cu(S{sub 4}){sub 2}]{center_dot}NH{sub 3}, [Yb(NH{sub 3}){sub 8}][Ag(S{sub 4}){sub 2}]{center_dot}2NH{sub 3}, and [La(NH{sub 3}){sub 9}][Cu(S{sub 4}){sub 2}] in supercritical ammonia: Metal sulfide salts of the first homoleptic lanthanide ammine complexes
- Clemson Univ., SC (United States)
Three new lanthanide metal polysulfides have been synthesized in supercritical ammonia: [Yb(NH{sub 3}){sub 8}][Cu(S{sub 4}){sub 2}]{center_dot} NH{sub 3} (I), [Yb(NH{sub 3}){sub 8}][Ag(S{sub 4}){sub 2}]{center_dot}2NH{sub 3} (II), [La(NH{sub 3}){sub 9}][Cu(S{sub 4}){sub 2}] (III). Compounds were prepared in sealed quartz tubes which were filled to one-third volume with liquid ammonia and heated at 170 {degrees}C for 3 days. Compounds I and II were obtained from the reaction of a premade ytterbium polysulfide with M and S in the ratio of 1:1:4, while [La(NH{sub 3}){sub 9}][Cu(S{sub 4}){sub 2}], III, was obtained by reacting La, Cu and S in the ratio of 1:1:8. In all these compounds, the lanthanide cation is coordinated only by ammonia, while the M{sup +} is chelated by S{sub 4}{sup 2-} to form metal tetrasulfide rings. [Yb(NH{sub 3}){sub 8}][Cu(S{sub 4}){sub 2}]{center_dot}NH{sub 3} and [Yb(NH{sub 3}){sub 8}][Ag(S{sub 4}){sub 2}]{center_dot}2NH{sub 3} contain [M(S{sub 4}){sub 2}]{sup 3-} anionic units with M{sup +} in a distorted tetrahedral coordination environment chelated by two S{sub 4}{sup 2-} groups. Compound III, [La(NH{sub 3}){sub 9}][Cu-(S{sub 4}){sub 2}], also contains anionic [Cu (S{sub 4}){sub 2}]{sup 3-} units; however, Cu{sup +} is in a trigonal planar coordination geometry due to the presence of one monodentate S{sub 4}{sup 2-}. All the compounds are unstable with respect to loss of ammonia, and decomposition yielded known ternary and binary phases.
- OSTI ID:
- 513364
- Journal Information:
- Inorganic Chemistry, Vol. 35, Issue 26; Other Information: PBD: 18 Dec 1996
- Country of Publication:
- United States
- Language:
- English
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