Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)(2)(μ,η(6):η(6)-P(6))] Towards the “Naked” Cations Cu(+), Ag(+), and Tl(+)

Although the cyclo-P(6) complex [(Cp*Mo)(2)(μ,η(6):η(6)-P(6))] (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-P(10) 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-P(6) 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.