Reactivity of the rhenium(V)–oxo complex [AsPh4][ReOCl4] toward bis(diphenylphosphino)amine NH(PPh2)2. Synthesis and crystal structures

Abstract

The complexes [ReCl₃(H₂O){NH(OPPh₂)PPh₂-P,O}]1, [ReCl₄{NH(OPPh₂)PPh₂-P,O}]3 and [AsPh₄][ReCl₄{N(OPPh₂)PPh₂-P,O}]4 were obtained by treatment of [AsPh₄][ReOCl₄] with NH(PPh₂)₂ under different experimental conditions. Their structures were determined by X-ray crystallography. In all complexes the co-ordination is nearly octahedral where a molecule of the ligand binds to rhenium through a phosphorus and oxygen. The Re–O distances, which range from 2.054(3) to 2.071 (6) A indicate the presence of neutral or partially negatively charged oxygens. The Re–Cl bond distances trans to oxygen are strongly related to the oxygen charge and hybridization.