Copper, Indium, Tin, and Lead Complexes with Fluorinated Selenolate Ligands: Precursors to MSex

Kareem Holligan, Patrick Rogler, David Rehe, Michael Pamula, Anna Y. Kornienko, Thomas J. Emge, Karsten Krogh-Jespersen, John G. Brennan

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

Reductive cleavage of C6F5SeSeC6F5 with elemental M (M = Cu, In, Sn, Pb) in pyridine results in the formation of (py)4Cu2(SeC6F5)2, (py)2In(SeC6F5)3, (py)2Sn(SeC6F5)2, and (py)2Pb(SeC6F5)2. Each group adopts a unique structure: the Cu(I) compound crystallizes as a dimer with a pair of bridging selenolates, two pyridine ligands coordinating to each Cu(I) ion, and a short Cu(I)-Cu(I) distance (2.595 Å). The indium compound crystallizes as monometallic five-coordinate (py)2In(SeC6F5)3 in a geometry that approximates a trigonal bipyramidal structure with two axial pyridine ligands and three selenolates. The tin and lead derivatives (py)2M(SeC6F5)2 are also monomeric, but they adopt nearly octahedral geometries with trans pyridine ligands, a pair of cis-selenolates, and two "empty" cis-positions on the octahedron that are oriented toward extremely remote selenolates (M-Se = 3.79 Å (Sn), 3.70 Å (Pb)) from adjacent molecules. Two of the four compounds (Cu, In) exhibit intermolecular π-π stacking arrangements in the solid state, whereas the stacking of molecules for the other two compounds (Sn, Pb) appears to be based upon molecular shape and crystal packing forces. All compounds are volatile and decompose at elevated temperatures to give MSex and Se(C6F5)2.The electronic structures of the dimeric Cu compound and monomeric (py)2M(SeC6F5)2 (M = Sn, Pb) were examined with density functional theory calculations.

Original languageEnglish (US)
Pages (from-to)8896-8904
Number of pages9
JournalInorganic Chemistry
Volume54
Issue number18
DOIs
StatePublished - Aug 20 2015

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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