The vibrational spectra of the cyanide ligand revisited: terminal cyanides.

A comparison is made between the vibrational characteristics of the carbonyl and cyanide ligands. There are significant differences; the latter has a smaller dipole moment and a larger quadrupole moment associated with the bond stretch. This quadrupole moment may be linked to the observation that the totally symmetric nu(CN) mode does not lie at the highest frequency for some cyanide complexes. There are problems with the pi-bonding model commonly used to interpret the nu(CN) data. For instance, for the first transition row hexacyanoanions, the spectra are almost independent of t2g occupancy but are very sensitive to the formal charge. It is suggested that the observed nu(CN) frequency shifts on complex formation are in large measure determined by the effective charge on the cation to which the cyanide group is attached, and a new model, the Internal Vibrational Stark Effect, is suggested to account for this. The model is supported by DFT calculations. Raman spectra of some cubic cyano species are reported, along with polarization and intensity data.