Uranium complexes of cyclic O,O-bidentate ligands with the P–N–P backbone
摘要:
The formation of uranium complexes of novel ligands belonging to phosphorylated 2-oxo-1,2-azaphospholane series, namely 2-ethoxy-1-diethoxyphosphoryl-2-oxo-1,2 lambda(5)-azaphospholane (1a) and both individual R*,R*- and R*,S*-diastereomers of the related 2-oxo-2-phenyl-1,2 lambda(5)-azaphospholanes 1b,c with different surrounding at the exocyclic phosphorus atom, has been studied. The structures of the complexes of ML composition obtained in the reaction with uranyl nitrate in 1:1 ratio were found to depend on the difference in donor properties of the oxygen atom of endo- and exocyclic phosphoryl groups. The ligand 1a possessing the greater difference, serves as O-monodentate one with metal-oxygen bonding via the endocyclic P=O function while both isomers of 1b, c coordinate to uranyl cation in a O,O-bidentate fashion. In solutions the ML complexes reacted with air oxygen to afford (mu(2)-peroxo)-bridged uranium complexes [{UO2(L)NO3}(2)(mu(2)-O-2)] which structures were confirmed by X-ray crystallography data. (C) 2011 Elsevier B.V. All rights reserved.
N-Phosphoryl-2-oxo-1,2-azaphospholanes: First Example of Cyclic O,O-Bidentate Ligands with the P-N-P Backbone
摘要:
A convenient one-pot synthesis of N-phosphoryl-2-oxo-1,2-azaphospholanes was developed starting from commercially available or simple-to-prepare phosphorus (III) acid chlorides and 3-bromopropylamine. The compounds readily form complexes with f-elements of ML, ML2, and M2L3 composition including (mu 2-peroxo)-bridged uranium complexes, depending on both the ligand and metal nature.
Facile One-Pot Synthesis and X-ray Characterization of N-(Thio)phosphoryl-2-oxo-1,2-azaphospholanes: First Example of Cyclic O,O- and O,S-Bidentate Ligands with the P-N-P Backbone
A convenient one-pot synthesis of N-phosphoryl- and N-thiophosphoryl-2-oxo-1,2-azaphospholanes was developed, starting from commercially available or simple-to-prepare phosphorus(III) acid chlorides and (3-bromopropyl)amine hydrobromide. The method is based on the intramolecular Arbuzov reaction of bis-phosphorus(III)-substituted N-(3-bromopropyl)amines generated in turn by double phosphorylation of