Phosphaniminato-komplexe von rhenium(VII). Synthesen und kristallstrukturen von [ReO₃(NPR₃)] (R = Ph, Et) sowie von [ReO(OSiMe₃)₃(Me₃SiNPEt₃)]

The phosphoraneiminato complexes [ReO₃(NPR₃)] with R = Ph (1) and R = Et (2) are made from dirhenium heptaoxide and the silylated phosphoraneimines Me₃SiNPR₃. The complexes 1 and 2 as well as the red silanolate [ReO(OSiMe₃)₃(Me₃SiNPEt₃)] (3), which is formed as a by-product in the synthesis of 2, are characterized crystallographically. 1 and 2 are monomeric molecules, in which the phosphoraneiminato ligands NPR₃^- realize short ReN bonds of 179.3 pm (1) and 178.6 pm (2), respectively, with large ReNP bond angles of 162.0° (1) and 160.6° (2), respectively. In the rhenium(V) complex 3 the oxoligand occupies the apical position of the tetragonal pyramidal coordination of the rhenium atom, while the oxygen atoms of the Me₃SiO^- groups take the basic positions along with the nitrogen atom of the phosphaneimine molecule.