Ability of fullerenes to act as ?6 ligands in transition metal complexes. A comparative PM3(tm)-density functional theory study

Autor: Dennis S. Marynick, Sor-Koon Goh
Rok vydání: 2001
Předmět:
Zdroj: Journal of Computational Chemistry. 22:1881-1886
ISSN: 1096-987X
0192-8651
DOI: 10.1002/jcc.1138
Popis: High-quality DFT calculations are employed to estimate the arene exchange energies for reactions of general formula: For C60 and C70 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. C70 is shown to be a slightly better arene ligand than C60; however, no enhancements of arene-like bonding capabilities are seen for C78 and C84 relative to C70. 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
Databáze: OpenAIRE
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