Preparation, structure, solid state and gas phase stability of the mixed neodymium nitrate–chloride complex NdCl(NO 3) 2{[(MeO) 2PO] 2C(OH) t Bu} 2

• Published in: Inorganica Chimica Acta 2006-03, Vol.359 (4), p.1329-1334
• Main Authors: Lees, Anthony M.J., Kresinski, Roman A., Platt, Andrew W.G.
• Format: Article
• Language: English
• Subjects: Bisphosphonate; Dealkylation; Mass spectra; Neodymium chloride; Nitrate; Structure
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2005.09.037

Nd(NO 3) 2ClL 2 is stable; Nd(NO 3)Cl 2L 2 and NdCl 3L 2 are unstable and cannot be isolated due to loss of methyl nitrate. The preparation and structure of the mixed anion complex NdCl(NO 3) 2{[(MeO) 2PO] 2C(OH) t Bu} 2 are reported. Single crystal X-ray diffraction shows that the bisphosphonate is bonded via both phosphoryl groups and the nitrates act as bidentate ligands. Intramolecular H-bonding is seen between the OH and the coordinated nitrate and chloride ligands. Thermal decomposition in the solid state is by loss of methyl nitrate. Electrospray mass spectrometry shows that loss of chloride is preferred over loss of nitrate in the gas phase. Attempted preparation of NdCl 2(NO 3){[(MeO) 2PO] 2C(OH) t Bu} 2 leads to the formation of a product approximating to [Nd{ t Bu(OH)C(PO 3H 2) 2} 2] 2H · NO 3 · (PO 4H 2) 2. Electrospray mass spectrometry and elemental analysis confirm the presence of the [ t Bu(OH)C(PO 4H 2) 2] − in the decomposition products.