A rare-earth-mediated conversion of white phosphorus into PBn3 and highly functionalized norbornane-P7

Abstract

The treatment of rare-earth metal dialkyl complexes Tp^Me2YBn₂(THF) (Bn = CH₂Ph, 1^Y) with P₄ in toluene at ambient temperature formed yttrium norbornane-BnP₇⁴⁻ (2^Y) and chain Bn₄P₆⁴⁻ (3^Y) complexes, accompanied by the formation of PBn₃ (I). However, only lutetium norbornane-BnP₇⁴⁻ complex 2^Lu and I were obtained from the reaction of 1^Lu with P₄ under the same conditions. Moreover, an atom-economic conversion of P₄ to PBn₃ and norbornane-BnP₇(Me₃Si)₄ (II) was also realized by the treatment of Tp^Me2LuCl₂(THF) with KBn, followed by a sequential reaction with P₄ and Me₃SiCl. These results indicated that P₄ functionalization using rare-earth dialkyl complexes can form not only novel rare-earth polyphosphorus complexes, but also organophosphorus compounds. All new compounds have been characterized by NMR spectroscopy and single-crystal X-ray diffraction studies.