Density Functional Study on the Electronic Structure of Trioxorhenium Organyls
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- 作者：Sibylle Kö ; stlmeier ; Oliver D. Hä ; berlen ; Notker Rö ; sch ; Wolfgang A. Herrmann ; Bahman Solouki ; and Hans Bock
- 刊名：Organometallics
- 出版年：1996
- 出版时间：April 2, 1996
- 年：1996
- 卷：15
- 期：7
- 页码：1872 - 1878
- 全文大小：200K
- 年卷期：v.15,no.7(April 2, 1996)
- ISSN：1520-6041
文摘
A linear combination of Gaussian-type orbital density functional(LCGTO-DF) investigationof three rhenium-oxo complexes, RReO3 (R =CH3, 
1-C6H5,5-C5H5), is presented,showingthe influence of the three different types of ligand-to-metal bonding
-alkyl, -aryl, and 
-aryl,respectively. The calculated ionization potentials of thesecompounds are compared to theirHe I photoelectron spectra and found to be in excellent agreement.In particular, the presentresults for H3C-ReO3 are much improved overvarious other theoretical approaches. Specialattention is drawn to the -ReO3 fragment energy levelsand to the nonbonding 2p lone pairson the oxygen atoms; their relative energetic positioning allowsconclusions on the chargedistribution and thus on the Lewis acidity of the rhenium atom in theactive site -ReO3.To assist this interpretation, Mulliken fragment charges andcalculated dipole momentsare discussed. A recently proposed relationship between the oxygencharge within the -ReO3fragment and 17O NMR shifts is supported.
1-C6H5,5-C5H5), is presented,showingthe influence of the three different types of ligand-to-metal bonding-alkyl, -aryl, and -aryl,respectively. The calculated ionization potentials of thesecompounds are compared to theirHe I photoelectron spectra and found to be in excellent agreement.In particular, the presentresults for H3C-ReO3 are much improved overvarious other theoretical approaches. Specialattention is drawn to the -ReO3 fragment energy levelsand to the nonbonding 2p lone pairson the oxygen atoms; their relative energetic positioning allowsconclusions on the chargedistribution and thus on the Lewis acidity of the rhenium atom in theactive site -ReO3.To assist this interpretation, Mulliken fragment charges andcalculated dipole momentsare discussed. A recently proposed relationship between the oxygencharge within the -ReO3fragment and 17O NMR shifts is supported.