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Abstract
Reactions designed to give Se6[Sb(OTeF5)6]2 by the reaction of Se2Br2, 4Se, and 2Ag[Sb(OTeF5)6] lead to products that include [Ag2(Se6)(SO2)2][Sb(OTeF5)6]2(1). The distorted cubic (Ag2Se6 2+) n consists of a Se6 molecule bicapped by two silver cations (local D3d sym.). Reactions of AgMX6 (M = As, Sb) with selenium in liquid SO2 yielded crystals of [Ag2Se6][AsF6]2 (2) and [AgSe6][Ag2(SbF6)3] (3). Both salts contain stacked arrays of [AgSe6]+ half-sandwich cationic units. [Ag2Se6][AsF6]2 in addition contains stronger, linear Se─Ag─Se horizontal linkages between the vertically stacked cationic columns. [AgSe6][Ag2(SbF6)3] features a remarkable three-dimensional [Ag2(SbF6)3]− anion held together by strong Sb─F···Ag contacts between component Ag+ and SbF6 − ions. Hexagonal channels through this honeycomb-like anion are filled by the stacked [AgSe6 +]x.
This work was supported by the Natural Science and Engineering Research Council of Canada NSERC (J.P.). Dr. Ingo Krossing is grateful to the Alexander von Humboldt Foundation in Bonn, Germany, for providing a Feodor-Lynen Fellowship. Dr. Folker Steden thanks DAAD for providing a doctoral fellowship (Hochschulprogramms III von Bund und Ländern).
