Preparation and structural properties of macrocyclic phosphonamides. Structural characterization of a potassium complex

A novel class of organophosphorus macrocycles containing one phosphonamide or one thiophosphonamide group was obtained by condensation of bis(dimethylamino)methyl-phosphine with the appropriate oligoether-bisprimary amine, followed by the oxidation of the P(III) species. The structures of two macrocyclic phosphonamide ligands (3 and4) which differ in the length of the oligoether chain, and that of the potassium thiocyanate complex of4, were studied by Xray diffraction. The crystals of3 and4 containe two crystallographically independent molecules. A cavity appears in the centre of each uncomplexed molecule, but the oxygen atoms of the longer oligoether chain are better oriented towards the centre of this cavity. An important rearrangement of the molecular conformation of4 occurs upon complexation as shown in the crystal structure analysis of the complex4· KSCN. The phosphoryl O atom of one molecule binds to the metal ion of another complexed molecule, leading to the self assembly of4· KSCN complexes.Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP. 82161 (27 pages).Research fellow (1986–1989), Université J. Fourier, Grenoble (France)