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

GHOLIVAND, KHODAYAR; MOSTAANZADEH, HOSSEIN; KOVAL, T.; DUSEK, M.; ERBEN, MAURICIO FEDERICO; STOECKLI-EVANS, HELEN; DELLA VÉDOVA, CARLOS OMAR

ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE

WILEY-BLACKWELL PUBLISHING, INC

Año: 2010 vol. 66 p. 441 - 450

0108-7681

New phosphoramidates with the formula RC(O)N(H)P(O)X2, R = 2-NO2—C6H4, 3-NO2—C6H4 and 4-NO2—C6H4, X = N(CH2CH3) (1)–(3), NC4H8 (4)–(6), and NC4H8O (7)–(9) were synthesized and characterized by 1H, 13C, 31P NMR and IR spectroscopy, and elemental analysis. The reaction of (9) with hydrated lanthanide(III) nitrate leads to ten- or ninecoordinated 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.