A series of easily accessible diphosphane compounds 1−4, based on bisphenol A derived backbones, has been prepared. A straightforward two‐step synthetic route has been employed to obtain these new ligands in good yields from cheap starting materials. Molecular structures for both compound 2 and its oxidized form (5·H2O) have been determined and are discussed in detail. The coordination of ligand 2 to palladium, platinum, and rhodium precursors has been studied by NMR spectroscopy as well as X‐ray crystallography. The molecular structures of the face‐to‐face dimeric species [{PdCl(CH3)(2)}2] (6), [{PtCl2(2)}2] (7), and [{RhCl(CO)(2)}2] (8) are described in detail. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)