| Autor: |
Kostlmeier, S., Haberlen, O. D., Rosch, N., Herrmann, W. A., Solouki, B., Bock, H. |
| Zdroj: |
Organometallics; April 2, 1996, Vol. 15 Issue: 7 p1872-1878, 7p |
| Abstrakt: |
A linear combination of Gaussian-type orbital density functional (LCGTO-DF) investigation of three rhenium−oxo complexes, RReO3 (R = CH3, η1-C6H5, η5-C5H5), is presented, showing the influence of the three different types of ligand-to-metal bonding σ-alkyl, σ-aryl, and π-aryl, respectively. The calculated ionization potentials of these compounds are compared to their He I photoelectron spectra and found to be in excellent agreement. In particular, the present results for H3C−ReO3 are much improved over various other theoretical approaches. Special attention is drawn to the −ReO3 fragment energy levels and to the nonbonding 2p lone pairs on the oxygen atoms; their relative energetic positioning allows conclusions on the charge distribution and thus on the Lewis acidity of the rhenium atom in the active site −ReO3. To assist this interpretation, Mulliken fragment charges and calculated dipole moments are discussed. A recently proposed relationship between the oxygen charge within the −ReO3 fragment and 17O NMR shifts is supported. |
| Databáze: |
Supplemental Index |
| Externí odkaz: |
|
