Copper, Indium, Tin, and Lead Complexes with Fluorinated Selenolate Ligands: Precursors to MSex
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- 作者：Kareem Holligan ; Patrick Rogler ; David Rehe ; Michael Pamula ; Anna Y. Kornienko ; Thomas J. Emge ; Karsten Krogh-Jespersen ; John G. Brennan
- 刊名：Inorganic Chemistry
- 出版年：2015
- 出版时间：September 21, 2015
- 年：2015
- 卷：54
- 期：18
- 页码：8896-8904
- 全文大小：473K
- ISSN：1520-510X
文摘
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)鈥揅u(I) distance (2.595 脜). 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 鈥渆mpty鈥?cis-positions on the octahedron that are oriented toward extremely remote selenolates (M鈥揝e = 3.79 脜 (Sn), 3.70 脜 (Pb)) from adjacent molecules. Two of the four compounds (Cu, In) exhibit intermolecular 蟺鈥撓€ 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.