Versatile solid-state coordination chemistry of telluroether complexes of silver(i) and copper(i)

Abstract

The treatment of EPh₂ (E = Te, Se) with Ag(O₃SCF₃) or Cu(O₃SCF₃)·1/2C₆H₆ in dichloromethane yields isomorphous complexes [Ag(TePh₂)₃](O₃SCF₃) (1), [Cu(TePh₂)₃](O₃SCF₃) (2), and [Cu(SePh₂)₃](O₃SCF₃) (3). The related reaction of TeTh₂ (Th = 2-thienyl, C₄H₃S) with Cu(O₃SCF₃)·1/2C₆H₆ affords [Cu(TeTh₂)₃](O₃SCF₃) (4). While not isomorphic with 1–3, its crystal structure bears a close relationship with them. The reaction of TeTh₂ or SePh₂ with Ag(O₃SCF₃) yields [Ag(TeTh₂)₂](O₃SCF₃) (5) and [Ag(SePh₂)₂](O₃SCF₃) (6), respectively. They form dinuclear complexes, the silver centers of which are coordinated to two terminal R₂E ligands and linked together by two bridging CF₃SO₃⁻ ligands. The dinuclear complexes further form supramolecular networks through π–π stacks of the aromatic rings. The treatment of Ag(O₃SCF₃) with Te(CH₂SiMe₃)₂ results in the formation of a mixture containing polynuclear [Ag{Ag[Te(CH₂SiMe₃)₂]}₄]_n(O₃SCF₃)_5n (7) and [Ag{Te(CH₂SiMe₃)₂}]_n(O₃SCF₃)_n (8). The cyclic repeating units in 7 are connected to polymeric chains by two bridging CF₃SO₃⁻ ligands. 8 contains a [–Ag–Te(CH₂SiMe₃)₂–]_n polymer. There are only weak van der Waals interactions between the polymer chains of 7 and 8.