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

The treatment of EPh2 (E = Te, Se) with Ag(O3SCF3) or Cu(O3SCF3)center dot 1/2C(6)H(6) 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)center dot 1/2C(6)H(6) 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 pi-pi 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.