Phosphanimin‐Derivate des Osmium(IV): Kristallstrukturen von trans‐[OsCl₄(HNPEt₃)₂] und (H₂NPPh₃)₂[OsCl₆]·2CH₃CN

Abstract

trans-[OsCl 4 (HNPEt 3 ) 2 ] (1) was prepared by reaction of osmium pentachloride with the silylated phosphoraneimine Me 3 SiNPEt 3 in dichloromethane solution forming yellow moisture sensitive single crystals. The hexachloroosmate(IV) (H 2 NPPh 3 ) 2 [OsCl 6 ]·2CH 3 CN (2) was obtained as yellow single crystals from osmium pentachloride and N-chlorotriphenylphosphoraneimine, ClNPPh 3 , in acetonitrile solution. 1 and 2 are characterized by IR spectroscopy and single crystal X-ray structure determinations.

The Reaction Chemistry of Plutonyl(VI) Chloride Complexes with Triphenyl Phosphineoxide and Triphenyl Phosphinimine

“…The anion, [PuO 2 Cl 4 ] 2− , has previously been structurally characterized by Wilkerson et al, as the dicesium salt, and is composed of the classical linear O−Pu−O actinyl moiety surrounded by four chloride ligands in the equatorial plane ( D 4 h symmetry). The Pu−O (1.709(10) and 1.718(9) Å) and Pu−Cl (2.641(4)−2.661(4) Å) bond lengths and O−Pu−O (178.6(4)°), O−Pu−Cl (88.2(3)−91.7(3)°) and Cl−Pu−Cl (85.71(11)−93.95(11)°) angles are all comparable to those reported by Wilkerson et al There are two crystallographically distinct [Ph 3 PNH 2 ] + cations, with the two P−N bond distances (1.624(11)−1.625(11) Å) the same, within errors, as the values obtained for the P−N bonds in [H 2 NPPh 3 ] 2 [OsCl 6 ]·2CH 3 CN (1.627(9) and 1.64(1) Å) . The phosphonium cations interact with the [PuO 2 Cl 4 ] 2− anion through N−H···Cl hydrogen-bonding interactions, with each chloride ligand interaction with a different phosphonium hydrogen atom (one short, 2.08 Å, and three long, 2.52, 2.56, and 2.54 Å, interactions in total).…”