Abstract
Mössbauer spectra of anhydrous ferricyanic acid, H 3Fe(CN) 6, and alkali metal ferricyanides, M 3[Fe(CN) 6]. xH 2O (where M Li, Na, Rb, Cs, NH 4 and Ag), have been studied at room temperature. These compounds show a two line spectrum indicating definite quadrupole splitting ( ΔE Q ). The values of ΔE Q range from 0·20 to 0·76 mm/sec. The isomer shifts (δ) vary from 0·08 to 0·26 mm/sec. (relative to sodium nitroprusside dihydrate). The isomer shift shows generally a decreasing trend with the increase in the electronegativity of the substituent cation. It is suggested that the cations influence the π-acceptor property of the cyanide ligands. The s-electron density at the iron nucleus increases as the π-acceptor nature of the ligand increases. The quadrupole splitting data is also consistent with this interpretation. A linear relationship is observed between δ and ΔE Q . The isomer shift for H 3Fe(CN) 6 is comparatively high presumably due to the presence of intermolecular hydrogen bonding in this compound.
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