Palladium(II) complexes of bis(diphosphene) with different coordination behaviors.

Organophosphorus compounds possessing a P-P double-bond character are intriguing materials in coordination chemistry because it is possible to form a variety of coordination modes from the π-bond in addition to the lone pairs. We report herein the complexation of a new bidentate ligand, ethylene-tethered bis(binaphthyldiphosphene) (S,S)-2, with palladium(II) species. The reaction of (S,S)-2 with [Pd(π-allyl)(cod)](SbF6) and PdCl2(cod) afforded η1/η1-bis(diphosphene) complex 7 and η1-diphosphene/η2-phosphanylphosphide complex 8, respectively. The latter was characterized by a chloride migration from the palladium atom to a phosphorus atom due to the high electron-accepting character of the PP moiety. Theoretical calculations revealed the migration process and nature of complex 8.

1,1'-Binaphthyl-substituted diphosphene: synthesis, structures, and chiral optical properties.

1,1'-Binaphthyl-substituted diphosphene 1 possessing a P[double bond, length as m-dash]P double bond and an axially chiral 1,1'-binaphthyl group was synthesized and fully characterized. Diphosphene 1 was prepared as an optically active form and thus is the first example of a chiral diphosphene. The CD spectra of 1 showed apparent circular dichroism in the longer wavelength region, caused by the P[double bond, length as m-dash]P moiety.