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Vibrational Spectroscopy of Compounds with Very Short Hydrogen Bonds. The Aqueous Bisformate Ion. Comparison with Two Solid Salts, and Some Comments on Broad OH Absorption Continua

Ernest Spinner ; Medical Chemistry Group, Australian National University, Canberra, A. C. T. 2601, Australia

Puni tekst: engleski pdf 28.656 Kb

str. 249-269

preuzimanja: 83



The infrared and Raman spectra of aqueous bisformate ions
(HC02)2ff, (HC02)2D-, (DC02)ff, (DC02)2D-, and of the isotopic
mixture (HC02) (DC02)H- are reported. For hydroxyl stretching
YOH = YOD = 1400 cm-1 (cf. ca. 1100 cm-1 in the solid Na+ and ca.
1400 cm-1 in the K+ salt). All the bands expected for a formate ion
moiety and most of those expected for a formic acid moiety appear
in both the infrared and the Raman spectrum (as for the solid
Na+ salt). Essentially unmodified formate ion is complexed with
appreciably modified formic acid and the complex does not possess
the centrosymmetric C21i structure predicted for it by a recent
ab initio molecular orbitals calculation, nor a centrosymmetric
OHO bond.

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