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)·1/2C6H6 in dichloromethane yields isomorphous complexes Ag(TePh2)3 (1), Cu(TePh2)3 (2), and Cu(SePh2)3 (3). The related reaction of TeTh2 (Th = 2-thienyl, C4H3S) with Cu(O3SCF3)·1/2C6H6 affords Cu(TeTh2)3 (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 (5) and Ag(SePh2)2 (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.