Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in [(Cp*Mo)2(μ, η6:η6‐P6)] Towards the "Naked" Cations Cu+, Ag+, and Tl+. Issue 44 (4th September 2015) - Fleischmann, Martin
Abstract: 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. Abstract : One ring to bind them all ! The reactivity of the long‐known hexaphosphabenzene complex 1 has been studied for the first time. The coordination of 1 to Cu +, Ag +, and Tl + affords layered compounds as supramolecular analogues of graphene, while oxidation leads to a bisallylic distortion of the P6 ring. A cyclo ‐P10 complex 2 was also characterized, which is the largest known cyclic polyphosphorus complex.