cyclo‐P4 Building Blocks: Achieving Non‐Classical Fullerene Topology and Beyond

The cyclo-P4 complexes [CpR Ta(CO)2 (η4 -P4 )] (CpR : Cp''=1,3-C5 H3 tBu2 , Cp'''=1,2,4-C5 H2 tBu3 ) turned out to be predestined for the formation of hollow spherical supramolecules with non-classical fullerene-like topology. The resulting assemblies constructed with CuX (X=Cl, Br) showed a highly symmetric 32-vertex core of solely four- and six-membered rings. In some supramolecules, the inner cavity was occupied by an additional CuX unit. On the other hand, using CuI, two different supramolecules with either peanut- or pear-like shapes and outer diameters in the range of 2-2.5 nm were isolated. Furthermore, the spherical supramolecules containing Cp''' ligands at tantalum are soluble in CH2 Cl2 . NMR spectroscopic investigations in solution revealed the formation of isomeric supramolecules owing to the steric hindrance caused by the third tBu group on the Cp''' ligand. In addition, a 2D coordination polymer was obtained and structurally characterized.