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.
Keywords: hexaphosphabenzene; inorganic graphene; polyphosphorus complexes; solvent-controlled reactivity; weakly coordinating anions.
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