Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)2(μ,η6:η6-P6)] Towards the “Naked” Cations Cu+, Ag+, and Tl+

Although the cyclo-P6 complex [(Cp*Mo)2 (μ,η(6) :η(6) -P6 )] (1) was reported 30 years ago, little is known about its chemistry. Herein, we report a high-yielding synthesis of 1, the complex 2, which contains an unprecedented cyclo-P10 ligand, and the reactivity of 1 towards the "naked" cations Cu(+) , Ag(+) , and Tl(+) . Besides the formation of the single oxidation products 3 a,b which have a bisallylic distorted cyclo-P6 middle deck, the [M(1)2 ](+) complexes are described which show distorted square-planar (M=Cu(4 a), Ag(4 b)) or distorted tetrahedral coordinated (M=Cu(5)) M(+) cations. The choice of solvent enabled control over the reaction outcome for Cu(+) , as proved by powder XRD and supported by DFT calculations. The reaction with Tl(+) affords a layered two-dimensional coordination network in the solid state.