Fluorinated Thiolates of Divalent and Trivalent Lanthanides. Ln−F Bonds and the Synthesis of LnF3

Fluorinated thiolates form particularly stable chalcogenolate complexes with the lanthanides. Both Sm(SC6F5)3 and Eu(SC6F5)2 were prepared by transmetalation. The Sm compound is a dimer in the solid state, with a pair of bridging thiolate ligands connecting the two Sm(III) ions, while the Eu(II) compound is polymeric. In both compounds there are clearly defined Ln−F interactions. Thermolysis of the Sm compound gives SmF3 and (C6F4S)n (n = 2, 3, 4).