• Cage compounds;
  • Ligand design;
  • Phosphorus;
  • Chirality;
  • Coordination modes


Diastereomeric Pd and Pt complexes with a highly rigid chelate cage ligand core have been designed on the basis of alkylated C2-symmetric tetra-tert-butylhexaphosphapentaprismanes R2P6C4tBu4. The ligands are accessible by substitution of the diiodo derivative I2P6C4tBu4 with Grignard and organyllithium reagents. Depending on the optical properties of the organyl group, racemic or diastereomeric dialkylhexaphosphapentaprismanes R2P6C4tBu4 can be treated with suitable PdII or PtII precursor complexes to form neutral square-planar cis-[(R2P6C4tBu4)PdCl2] and cis-[(R2P6C4tBu4)PtCl2] complexes, respectively. Monoalkylation products RIP6C4tBu4 were also observed in the reaction mixtures, but in most cases were inactive as chelate ligands towards PdII and PtII. For R = (S)-2-methylbutyl, the diastereomers of the PdCl2 complex were efficiently separated by column chromatography and crystallization to give the two diastereomers in up to >99 % de and they were fully characterized by NMR and CD spectroscopy as well as by X-ray diffraction analysis. The two diastereomers of cis-[{(S)-2-methylbutyl}2(P6C4tBu4)PdCl2] represent the first example of a pair of isolated optically active, C2-symmetric, square-planar PdII complexes with chelate P–C cage ligands. A square-planar Pd complex with two monoanionic RP6C4tBu4 cage ligands can be obtained from the monoallylation product (allyl)IP6C4tBu4. This reaction failed for the other monoalkylation products RIP6C4tBu4 and PtII.