9Be and 31P NMR analyses on the influence of imino groups on Be2+ complex stabilities of a series of cyclo‐μ‐imido triphosphate anions |
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Authors: | Hideshi Maki Masahiko Tsujito Hiroyuki Nariai Minoru Mizuhata |
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Affiliation: | Department of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, , 1‐1 Rokkodai‐cho, Nada‐ku, Kobe, 657‐8501 Japan |
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Abstract: | The complexation behaviors of Be2+ with cyclo‐μ‐imido triphosphate anions, cP3O9?n(NH)n3? (n = 1, 2), have been investigated by both 9Be and 31P NMR techniques at ?2.3 °C in order to clarify the coordination structures of the complexes. The spectra showed that cP3O9?n(NH)n (n = 1, 2) ligands form ML, ML2, and M2L complexes with Be2+ ions, and the formation of complexes coordinating with nitrogen atoms of the cyclic framework in the ligand molecule has been excluded. These complexation trends are very similar to those of Be2+‐cP3O6(NH)33? system, which has been reported by us. The peak deconvolution of 9Be NMR spectra made these beryllium complexes amenable to stability constant determinations. The stability constants of the complexes increase with an increase in the protonation constants of the ligands as the number of imino groups, which constitute the ligand molecules, is ascended. This increase is primarily attributable to the lower electronegativity of nitrogen atoms than oxygen atoms, which are directly bonded to central phosphorus atoms; moreover, tautomerism equilibrium in the entire of the imidopolyphosphate molecule is also responsible to the higher basicity. 31P NMR spectra measured concurrently have verified the formation of the complexes estimated by the 9Be NMR measurement. Intrinsic 31P NMR chemical shift values of the phosphorus atoms belonging to ligand molecules complexed with Be2+ cations have been determined. Not only the protonation constants but also the stability constants of all Be2+ complexes increase approximately linearly with an increase in the number of imino groups. Copyright © 2013 John Wiley & Sons, Ltd. |
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Keywords: | NMR 9Be imidophosphate beryllium peak deconvolution microscopic coordination stability constant tautomerism |
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