Redox and Coordination Behavior of the Hexaphosphabenzene Ligand in (Cp*Mo)2(μη6:η6-P6) Towards the Naked Cations Cu+ Ag+ and Tl+

摘要

Although the cyclo-P6 complex [(Cp*Mo)2(μ,η⁶:η⁶-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.