Polysulfide Coordination Clusters of the Lanthanides

• Published in: Angewandte Chemie International Edition Vol. 56; no. 43; pp. 13249 - 13252
• Main Authors: Ma, Ying‐Zhao, Bestgen, Sebastian, Gamer, Michael T., Konchenko, Sergey N., Roesky, Peter W.
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 16-10-2017
• Edition: International ed. in English
• Subjects: Clusters; coordination clusters; Dipping; Lanthanides; Polysulfides; Samarium; Sulfur; Toluene; ytterbium; samarium; sulfur; ytterbium; coordination clusters; lanthanides
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201707578

The reaction of [(DippForm)2Ln(thf)2] with an excess of elemental sulfur in toluene resulted in the formation of the trinuclear polysulfide coordination clusters [(DippForm)3Ln3S12] (Ln=Sm, Yb; DippForm=N,N′‐bis(2,6‐diisopropylphenyl)formamidinate). These are the first f element coordination clusters (LnnSx) with a larger polysulfide unit (n and x>2). The formation of the coordination clusters can be rationalized by the reductive cleavage of S8 with divalent lanthanides.
Stocking up on sulfur: The trinuclear polysulfide coordination clusters [(DippForm)3Ln3S12] (Ln=Sm, Yb; DippForm=N,N′‐bis(2,6‐diisopropylphenyl)formamidinate) were synthesized (see picture). They are the largest f element polysulfide coordination clusters with a larger polysulfide unit.