Ability of fullerenes to act as η6 ligands in transition metal complexes. A comparative PM3(tm)–density functional theory study
✍ Scribed by Sor-Koon Goh; Dennis S. Marynick
- Publisher
- John Wiley and Sons
- Year
- 2001
- Tongue
- English
- Weight
- 113 KB
- Volume
- 22
- Category
- Article
- ISSN
- 0192-8651
- DOI
- 10.1002/jcc.1138
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✦ Synopsis
Abstract
High‐quality DFT calculations are employed to estimate the arene exchange energies for reactions of general formula:
For C~60~ and C~70~ complexes of Cr(CO)~3~, full geometry optimizations at the DFT level using moderately large basis sets were performed, while for the other systems a hybrid approach was developed in which the geometries were obtained at the PM3(tm) level and the energetics were evaluated at the DFT level. C~70~ is shown to be a slightly better arene ligand than C~60~; however, no enhancements of arene‐like bonding capabilities are seen for C~78~ and C~84~ relative to C~70~. Explicit calculation of a series of exchange energies at the DFT level using both DFT and PM3(tm) geometries demonstrates that PM3(tm) geometries are sufficiently accurate for the calculation of energetics at a higher theoretical level, but PM3(tm) calculations are inadequate for a quantitative assessment of exchange energies. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1881–1886, 2001