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.
The reaction of 1-naphthyl bromide with n-butyl lithium, elemental tellurium, and 1,4-dibromobutane in THF affords both (CH)Te(CH)Te(CH) (1) and [(CH)Te(CH)]Br (2) in good yields. 1 is preferentially formed at low temperatures and is a rare example of a structurally characterized ditelluroether in which the tellurium atoms are bridged by a hydrocarbon chain. In the solid state, 1 shows secondary bonding TeTe interactions, which connect the molecules into layers which are further linked to 3-dimensional frameworks by TeH hydrogen bonds. [(CH)Te(CH)]Br (2) is formed concurrently during the synthesis of 1 and is the main product, when the reaction is carried out at room temperature. The revPBE/def2-TZVPP calculations of the reaction profiles indicate that the formation of 2 is somewhat more favourable than that of 1. Furthermore, at room temperature the activation energy for the formation of 2 is lower than that of 1. At low temperatures the activation energy of the reaction leading to 1 is lower than that to 2, which is consistent with the synthetic observations. When 1 was treated with CuBr, [Cu(μ-Br){μ-(CH)Te(CH)Te(CH)}] (3) was formed. It crystallizes as two polymorphs (3a) and (3b) in which both the packing and the conformation of the ditelluroether ligands are different. The reaction of 1 with HgCl produces [(CH)Te(CH)][HgCl]·CHCl (4·CHCl) and that of 1 with CuCl affords [(CH)Te(CH)]Cl (5). 2 and 5 are isomorphous.
TeI 2 (CH 2 SiMe 3 ) 2 (1), TeI 2 Th(CH 2 SiMe 3 Wiley Periodicals, Inc. Heteroatom Chem 22:348-357, 2011; View this article online at wileyonlinelibrary.com.Bis(trimethylsilylmethyl)tellane (0.094 g; 0.311 mmol) was dissolved in 3 mL of THF, and the Heteroatom Chemistry
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