Synthese und Struktur von Thiolatokomplexen des einwertigen Kupfers: Tetrameres und Octameres [CuSC6H2(i-Pr)3] / Synthesis and Structure of Thiolato Complexes of Monovalent Copper: Tetrameric and Octameric [CuSC6H2(i-Pr)3]

Abstract

[CuSC6H2(i-Pr)3]n = 4 (1), and n = 8 (2) are obtained from CuCO3 · Cu(OH)2 and 2,4,6-tri(isopropyl)thiophenol in a slow reaction, where long reaction times promote the formation of octameric 2.1 crystallizes as colorless platelets, space group C 2/c: a = 3647(2), b = 854.8(6), c = 2061.3(7) pm, β = 105.98(4)°, Ζ = 4. Central unit of the tetrameric complex with the symmetry C2 is a non planar eight-membered Cu–S heterocycle. The four Cu atoms form a rhombus with short edges of 269.7 and 270.1 pm. The bridging SR-ligands are arranged alternatingly above and below the Cu4 rhombus. Octameric 2 crystallies as 2•(H2O)x in the form of orthorhombic yellow blocks, space group Pbcn: a = 2513(1), b = 1975(1), c = 2747(1) pm, Z = 4. The thiolato ligands connect the Cu atoms to form a folded 16-membered Cu–S ring with the symmetry C2. The eight S atoms are arranged at the corners of a cube with the Cu atoms occupying eight of its edges. The Cu–Cu distances are in the range of 267.8 to 304.0 pm. In 1 as well as in 2 the Cu atoms are linearly coordinated with Cu–S distances of 214.7 to 217.9 pm.