Reactions of 1,1′‐Diphosphaferrocene with CuCl and CuBr Resulting in Cu 4 P 4 X 4 Fe 2 ( X = Cl, Br) Complexes with Adamantane‐like Topologies

Cu 4 P 4 X 4 Fe 2 ( X = Cl, Br) cages are formed upon reactions of octaethyl‐1,1′‐diphosphaferrocene (odpf) with the respective Cu I halide in CH 2 Cl 2 /CH 3 CN solvent mixtures. These cages have adamantoid Cu 4 X 4 P 2 cores with two planar anelated CuP 2 Fe rings as the flaps. Both complexes 1 and 2 feature tri‐ and tetracoordinate Cu I ions and an additional acetonitrile solvent molecule in the crystal. In 1 , the solvent molecule is coordinated to one copper ion whereas it remains uncoordinated in 2 . The tricoordinate Cu I ions show a slight pyramidalization at the metal atom and somewhat short contacts to the other tricoordinate Cu I ion in 2 or the Cu 3 ‐triangle in 1 . NMR spectroscopy revealed easy decoordination of the acetonitrile ligand from 1 and a dynamic “windshield‐wiper”‐type process that interconverts the differently coordinated phospholide rings of each odpf ligand and the tri‐ and tetracoordinate Cu I ions.