Polycyclic bis(amido)cyclodiphosphazane complexes of antimony(III) and bismuth(III): syntheses, molecular structures and solution behaviour

Abstract

Reactions of SbCl₃ and BiCl₃ with [(PNBu^t)₂(NRLi·THF)₂] (R = Bu^t, Ph) produced polycyclic cage complexes of the formula {[(PNBu^t)₂(NR)₂E]Cl}, (E = Sb, R = Bu^t 1a; E = Bi, R = Bu^t 2; E = Sb, R = Ph 3). The bis(tert-butylamido)cyclodiphosphazane complexes of antimony were further derivatized by the substitution of the chloride ligand with N₃ 1b, -OPh 1c, and N(SiMe₃)₂ 1d groups. Structural studies showed all compounds to have virtually isometric central polycyclic cages. In solution some of these complexes are fluxional, due to the heavier Group 15 elements pyramidal inversion between two equivalent cyclodiphosphazane ring sites. The activation energies for this process were determined to be a function of both metal and ligand.