The Potential of the Diarsene Complex [(C(5)H(5))(2)Mo(2)(CO)(4)(μ,η(2)‐As(2))] as a Connector Between Silver Ions

The reaction of the organometallic diarsene complex [Cp(2)Mo(2)(CO)(4)(μ,η(2)‐As(2))] (B) (Cp = C(5)H(5)) with Ag[FAl{OC(6)F(10)(C(6)F(5))}(3)] (Ag[FAl]) and Ag[Al{OC(CF(3))(3)}(4)] (Ag[TEF]), respectively, yields three unprecedented supramolecular assemblies [(η(2)‐B)(4)Ag(2)][FAl](2) (4), [(μ,η(1):η(2)‐B)(3)(η(2)‐B)(2)Ag(3)][TEF](3) (5) and [(μ,η(1):η(2)‐B)(4)Ag(3)][TEF](3) (6). These products are only composed of the complexes B and Ag(I). Moreover, compounds 5 and 6 are the only supramolecular assemblies featuring B as a linking unit, and the first examples of [Ag(I)](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.