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

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.