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The interactions of the coinage-metal cations Cu1+, Ag1+ and Au1+ with the (WSe4)2- anion are investigated via NMR spectroscopic and crystallographic studies. The reaction of a suspension of Cu2+, Ag2+ and Au2+ in CH3CN with (NPr4)2(WSe4) generates the compounds (mu-WSe4)((PMe2Ph)2Cu)2, (mu-WSe4)((PMe2Ph)2Ag)2 and (mu-WSe4)((PMe2Ph)2Au)2, respectively. The structure of (mu-WSe4)((PMe2Ph)2Cu)2 possesses a crystallographically imposed 2-fold axis, with the W center and the Cu atoms possessing a tetrahedral and distorted tetrahedral geometries, respectively.

(NEt4)2(WSe4) reacts with Li(CN)Cu(C4H3S) to form (NEt4)2(mu-WSe4)((SC4H3)SeCu)2, and Se is discharged by the decomposition of (WSe4)2-anion. The Se atom is inserted into copper-carbon bond of Cu(C4H3S) to produce 2-selenothiophene ligand. Crystallographic and spectroscopic analyses reveal the chemical properties of (WSe4)2 or coinage metal complexes and the process of selenium insertion. The nucleophilicity of 2-selenothiophene is also observed.

Presents the synthesis, NMR spectroscopy and crystal structure of a selenium insertion product. Reaction of a CH3CN solution with lithium; Crystallization with four formula units in the tetragonal space group; Full anisotropic refinement of the structure.