Trivalent lanthanide compounds with fluorinated thiolate ligands: Ln-F dative interactions vary with Ln and solvent

Jonathan H. Melman, Christa Rohde, Thomas J. Emge, John G. Brennan

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Abstract

The fluorinated tris-thiolate compounds Ln(SC6F5)3 can be isolated as THF, pyridine, or DME coordination complexes. In THF, the larger Ce forms dimeric [(THF)3Ce(SC6F5)3]2 (1) with bridging thiolate ligands, while the smaller lanthanides (Ln = Ho (2), Er (3)) form monometallic (THF)3Ln(SC6F5)3 compounds. There is a tendency for fluoride to coordinate to Ln throughout the lanthanide series (Ce-Er). The cerium compound 1 contains a pair of bridging thiolates connecting two eight-coordinate Ce(III) ions. Of the two terminal thiolates, only one exhibits a distinct Ce-F bond. In contrast, the Ho derivative (THF)3Ho(SC6F5)3 is a molecular compound in the solid state, with two monodentate thiolates and one thiolate that again coordinates through both S and F atoms. Incorporation of a stronger Lewis base reduces but does not necessarily eliminate the tendency to form Ln-F bonds. Structural characterization of the eight-coordinate (pyridine)4Sm(SC6F5)3 (4) reveals a single, clearly defined Ln-F interaction, while in (pyridine)4Yb-(SC6F5)3 (5) there are no Yb-F bonds. In the structure of (DME)2Er(SC6F5)3 (6) the DME ligands completely displace F from the Er coordination sphere.

Original languageEnglish (US)
Pages (from-to)28-33
Number of pages6
JournalInorganic Chemistry
Volume41
Issue number1
DOIs
Publication statusPublished - Jan 14 2002

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All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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