The metal carbonyl cluster species Ru3(CO)12 is of long-standing interest as a photochemical substrate and as a synthetic precursor: New high-level DFT calculations indicate (contrary to other calculations and long-held structural assumptions about this compound) that the typically presented D3h structure (a) is actually a transition state between lower-symmetry C2 structures (b) of slightly lower energies. High-quality IR and Raman spectra of Ru3(CO)12 in the CO stretching region were collected in solutions of varying solvent polarity, revealing both band splitting and extra bands consistent with a lower-symmetry structure. Temperature dependence of the IR spectrum additionally suggests dynamic exchange on the IR time scale between spectrally distinct populations. The effects of solvent on band positions in the vibrational spectra are substantial, indicating that the CO frequencies are modulated by the arrangement of solvent dipoles in the solvation sphere.

Ground-state vibrational dynamics in Ru<sub>3</sub>(CO)<sub>12</sub>

243rd National Meeting (2012)

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Ground-state vibrational dynamics in Ru3(CO)12

Ground-state vibrational dynamics in Ru₃(CO)₁₂