A Stable Bis(thiolate) of Copper(II) with Long Axial Copper-sulfur Linkages: Crystal and Molecular Structure of Trans-[Cu(cyclam)(SC₆F₅)₂]
With pentafluorothiophenolate in alcohol solvents, the (1,4,8,11-tetraazacyclotetradecane)copper(II) cation, Cu(cyclam)2+, is not reduced but yields the red complex Cu(cyclam)(SC6F5)2, which crystallizes in the space group P1. The cell constants are Z = 1, a = 7.140 Å, b = 8.320 Å, c = 12.033 Å, α = 75.02°, β = 88.97°, γ = 71.07°, V = 651 Å3, and ρobsd = 1.65 g cm-3, with Rw = 5.5%. The sexicoordinate complex is tetragonally elongated, with equatorial Cu-N bonds of 2.005, 2.011, 2.005, and 2.011 Å in a square arrangement. The axially disposed thiolate anions are weakly bonded, with Cu-S distances of 2.94 Å, comparable with the axial Cu-S bond in plastocyanin. The optical and ESR spectra of the complex reveal no characteristic effects of the axial thiolates on the electronic properties of the Cu(II) ion. © 1983 American Chemical Society.
A. W. Addison and E. Sinn, "A Stable Bis(thiolate) of Copper(II) with Long Axial Copper-sulfur Linkages: Crystal and Molecular Structure of Trans-[Cu(cyclam)(SC₆F₅)₂]," Inorganic Chemistry, American Chemical Society (ACS), Jan 1983.
The definitive version is available at https://doi.org/10.1021/ic00150a017
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