Abstract
The reaction of the organometallic diarsene complex [Cp2Mo2(CO)4(μ,η2‐As2)] (B) (Cp = C5H5) with Ag[FAl{OC6F10(C6F5)}3] (Ag[FAl]) and Ag[Al{OC(CF3)3}4] (Ag[TEF]), respectively, yields three unprecedented supramolecular assemblies [(η2‐B)4Ag2][FAl]2 (4), [(μ,η1:η2‐B)3(η2‐B)2Ag3][TEF]3 (5) and [(μ,η1:η2‐B)4Ag3][TEF]3 (6). These products are only composed of the complexes B and AgI. Moreover, compounds 5 and 6 are the only supramolecular assemblies featuring B as a linking unit, and the first examples of [AgI]3 units stabilized by organometallic bichelating ligands. According to DFT calculations, complex B coordinates to metal centers through both the As lone pair and the As−As σ‐bond thus showing this unique feature of this diarsene ligand.
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