title: Copper, indium, tin, and lead complexes with fluorinated selenolate ligands: precursors to MSex.
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.
authors: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey , New Brunswick, New Jersey 08903, United States.
authors: Kareem
authors: K
authors: Holligan
authors: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey , New Brunswick, New Jersey 08903, United States.
authors: Patrick
authors: P
authors: Rogler
authors: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey , New Brunswick, New Jersey 08903, United States.
authors: David
authors: D
authors: Rehe
authors: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey , New Brunswick, New Jersey 08903, United States.
authors: Michael
authors: M
authors: Pamula
authors: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey , New Brunswick, New Jersey 08903, United States.
authors: Anna Y
authors: AY
authors: Kornienko
authors: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey , New Brunswick, New Jersey 08903, United States.
authors: Thomas J
authors: TJ
authors: Emge
authors: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey , New Brunswick, New Jersey 08903, United States.
authors: Karsten
authors: K
authors: Krogh-Jespersen
authors: Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey , New Brunswick, New Jersey 08903, United States.
authors: John G
authors: JG
authors: Brennan