Complexes having metal-metal bonds from “superlong” to “supershort”, and with formal bond orders between zero and 4, are examined by vibrational spectroscopy of the ground and excited states, and by transient spectroscopies. Effects of temperature and extreme pressure are also examined. Electronic excitations having bonding-to-antibonding or antibonding-to-bonding character affect metal-metal and other vibrational frequencies in predictable directions, and specific structural information (bond distances) can be extracted via empirical bond distance-force constant relationships. Extreme pressure applied to quadruply-bonded [M2X8] complexes alters both vibrational and electronic potential surfaces, by direct compression and by pressure-dependent steric effects. Systems discussed include d4 (Cr(II), Mo(II), and Re(III)), d8 (Rh(I) and Pt(II)), and mixed-valence d9-d10 (Cu(I,II)) complexes.

Spectroscopic studies of metal-metal bonding

251st National Meeting (2016)

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