A cyclo‐P(6) Ligand Complex for the Formation of Planar 2D Layers

The all‐phosphorus analogue of benzene, stabilized as middle deck in triple‐decker complexes, is a promising building block for the formation of graphene‐like sheet structures. The reaction of [(CpMo)(2)(μ,η(6):η(6)‐P(6))] (1) with CuX (X=Br, I) leads to self‐assembly into unprecedented 2D networks of [{(CpMo)(2)P(6)}(CuBr)(4)](n) (2) and [{(CpMo)(2)P(6)}(CuI)(2)](n) (3). X‐ray structural analyses show a unique deformation of the previously planar cyclo‐P(6) ligand. This includes bending of one P atom in an envelope conformation as well as a bisallylic distortion. Despite this, 2 and 3 form planar layers. Both polymers were furthermore analyzed by (31)P{(1)H} magic angle spinning (MAS) NMR spectroscopy, revealing signals corresponding to six non‐equivalent phosphorus sites. A peak assignment is achieved by 2D correlation spectra as well as by DFT chemical shift computations.