title: Syntheses, spectroscopic study and X-ray crystallography of some new phosphoramidates and lanthanide(III) complexes of N-(4-nitrobenzoyl)-N',N''-bis(morpholino)phosphoric triamide.
abstract: New phosphoramidates with the formula RC(O)N(H)P(O)X(2), R = 2-NO(2)-C(6)H(4), 3-NO(2)-C(6)H(4) and 4-NO(2)-C(6)H(4), X = N(CH(2)CH(3)) (1)-(3), NC(4)H(8) (4)-(6), and NC(4)H(8)O (7)-(9) were synthesized and characterized by (1)H, (13)C, (31)P NMR and IR spectroscopy, and elemental analysis. The reaction of (9) with hydrated lanthanide(III) nitrate leads to ten- or nine-coordinated complexes, (10)-(13). The crystal structure has been determined for (3), (5), (9), (10) and (13). In contrast to all of the previously reported similar phosphoramidate compounds, the -C(O)-N(H)-P(O) skeleton in the free ligand (9) shows a cisoid conformation, with the C=O and P=O double bonds adopting a nearly syn conformation. Quantum chemical calculations were applied for clarifying this exceptional conformational behavior. The monodentate neutral ligand (9) is coordinated to the metal ions via the phosphoryl O atom, adopting the usual anti conformation between the C=O and P=O groups.
authors.affiliation: Department of Chemistry, Faculty of Basic Sciences, Tarbiat Modares University, Tehran, Iran. gholi_kh@modares.ac.ir
authors.forename: Khodayar
authors.initials: K
authors.lastname: Gholivand
authors.forename: Hossein
authors.initials: H
authors.lastname: Mostaanzadeh
authors.forename: Tomas
authors.initials: T
authors.lastname: Koval
authors.forename: Michal
authors.initials: M
authors.lastname: Dusek
authors.forename: Mauricio F
authors.initials: MF
authors.lastname: Erben
authors.forename: Helen
authors.initials: H
authors.lastname: Stoeckli-Evans
authors.forename: Carlos O
authors.initials: CO
authors.lastname: Della Védova
mesh_terms: D000577:Amides / Q000737:chemistry*; D018360:Crystallography, X-Ray; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009025:Morpholines / Q000737:chemistry*; D009578:Nitrobenzenes / Q000737:chemistry*; D010756:Phosphoric Acids / Q000737:chemistry*; D013055:Spectrophotometry, Infrared
chemical_list: D000577:Amides; D028581:Lanthanoid Series Elements; D008024:Ligands; D009025:Morpholines; C551338:N-(4-nitrobenzoyl)-N',N'-bis(morpholino)phosphoric triamide; D009578:Nitrobenzenes; D010756:Phosphoric Acids; C011067:phosphoramidic acid