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Structural study on 2,2'-(methylimino)bis($$N$$,$$N$$-dioctylacetamide) complex with Re(VII)O$$_{4}$$$$^{-}$$ and Tc(VII)O$$_{4}$$$$^{-}$$ by $$^{1}$$H-NMR, EXAFS and IR spectroscopy

Saeki, Morihisa; Sasaki, Yuji  ; Nakai, Ayaka*; Ohashi, Akira*; Banerjee, D.*; Scheinost, A. C.*; Foerstendorf, H.*

The structures of the complex of 2,2'-(methylimino)bis($$N$$,$$N$$-dioctylacetamide) (MIDOA) with M(VII)O$$_{4}$$$$^{-}$$ (M=Re and Tc), which were prepared by liquid-liquid solvent extraction, were investigated by using $$^{1}$$H-NMR, EXAFS and IR spectroscopy. The results from $$^{1}$$H-NMR and EXAFS provide therefore evidence of M(VII)O$$_{4}$$$$^{-}$$...H$$^{+}$$MIDOA complex formation in the organic solution. The IR spectra of Re(VII)O$$_{4}$$$$^{-}$$...H$$^{+}$$MIDOA and Tc(VII)O$$_{4}$$$$^{-}$$...H$$^{+}$$MIDOA were analyzed based on the structures and the IR spectra calculated at the B3LYP/cc-pVDZ level. Comparison of the observed and calculated IR spectra demonstrates that an intramolecular hydrogen bond is formed in H$$^{+}$$MIDOA and the M(VII)O$$_{4}$$$$^{-}$$ ion interact with H$$^{+}$$MIDOA through multiple C-H$$_{n}$$...O hydrogen bonds.

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Category:Chemistry, Inorganic & Nuclear

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