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The Raman spectra of the ions Co(CO)4—, Fe(CO)42—, and HFe(CO)4— have been studied in aqueous solutions of the corresponding sodium salts. The spectra of Co(CO)4— and Fe(CO)42—, excited by the helium radiations 5875.6 and 6678.1 A are in full agreement with the expected Td symmetry of these ions; all observed frequencies were assigned to fundamental vibrational modes. A normal coordinate treatment was carried out under the assumption of a simplified valence force field model making use of only two interaction constants. The values of the fundamental frequencies of the tetrahedral ions, calculated by means of the potential constants of this model, were found to be in satisfactory agreement with the observed Raman shifts. The Raman spectrum of HFe(CO)4—, put in correlation with that of Fe(CO)42—, points strongly to a C3v symmetry of the former ion.

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