Synthesis of arenethiolate complexes of divalent and trivalent lanthanides from metallic lanthanides and diaryl disulfides: Crystal structures of [(Yb(hmpa){sub 3}){sub 2}({mu}-SPh){sub 3}][SPh] and Ln(SPh){sub 3}(hmpa){sub 3} (Ln = Sm, Yb; hmpa = hexamethylphosphoric triamide)
- Osaka Univ. (Japan); and others
A convenient and one-pot synthetic method of lathanide thiolate compounds was developed. An excess of metallic samarium, europium, and ytterbium directly reacted with diaryl disulfides in THF to give selectively Ln(II) thiolate complexes, [Ln(SAr)({mu}-SAr)(thf){sub 3}]{sub 2} (1, Ln = Sm; 2, Ln = Eu; Ar = 2,4,6-triisopropylphenyl), Yb(SAr){sub 2}(py){sub 4} (3, py = pyridine), and [(Ln(hmpa){sub 3}){sub 2}({mu}-SPh){sub 3}][SPh] (6, Ln = Sm; 7, Ln = Eu; 8, Ln = Yb; hmpa = hexamethylphosphoric triamide). Reaction of metallic lanthanides with 3 equiv of disulfides afforded Ln(III) thiolate complexes, Ln(SAr){sub 3}(py){sub n}(thf){sub 3-n} (9a, Ln = Sm, n = 3, 9b, Ln = Sm, n = 2; 10, Ln = Yb, n = 3) and Ln(SPh){sub 3}(hmpa){sub 3} (11, Ln = Sm; 12, Ln = Eu; 13, Ln = Yb). Thus, Ln(II) and Ln(III) thiolate complexes were prepared from the same source by controlling the stoichiometry of the reactants. X-ray analysis of 8 revealed that 8 has the first ionic structure composed of triply bridged dinuclear cation and benezenethiolate anion.
- OSTI ID:
- 255629
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 1 Vol. 35; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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