Molybdenum (VI) dioxodihalides: Agreement with experiment and prediction of unknown properties through density functional theory
✍ Scribed by M. Torrent; P. Gili; M. Duran; M. Solà
- Publisher
- John Wiley and Sons
- Year
- 1997
- Tongue
- English
- Weight
- 177 KB
- Volume
- 61
- Category
- Article
- ISSN
- 0020-7608
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✦ Synopsis
Density functional calculations are reported for the molecular structures, harmonic Ž vibrational frequencies, UVrvisible spectra, and oxo-transferability of MoO X X s 2 2 . F, Cl, Br, I . Available experimental data have been used to check the validity of the theoretical calculations. Given the good agreement between theory and gas-phase experiment, predictions have been issued for the less studied members of this family of compounds. Furthermore, electronic spectra of the full series have been computed for the first time. For all transitions studied, excitation energies decrease in the order F ) Cl ) Br ) I. Finally, the labilization of MoᎏO bonds generated by the HOMOᎏLUMO transition, which is related to the oxygen-atom transfer reaction in the active site of molybdenum oxidoreductases, was also investigated. For MoO Cl and MoO Br 2 2 2 2 compounds, the HOMO᎐LUMO transition yields a considerable lengthening of the MoᎏO bond, yet not requiring a large excitation energy.