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Mechanistic Studies of Ligand Fluxionality in [Mo(ç5-Cp)(ç1-Cp)(L)2]n
Citation
Ariafard, A and Tabatabaie, ES and Yates, BF, Mechanistic Studies of Ligand Fluxionality in [Mo(c5-Cp)(c1-Cp)(L)2]n, The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 113, (12) pp. 2982-2989. ISSN 1089-5639 (2009) [Refereed Article]
Abstract
Density functional theory has been used to provide a thorough investigation of the mechanistic factors affecting Cp ligand fluxionality in a series of organometallic complexes, [M(η5-Cp)(η1-Cp)(L) 2]n, involving different metals, different oxidation states, and different ligands. Excellent agreement with experiment for the barrier heights for the 1,5-shift were obtained for the complexes [Fe(η5-Cp*)(η1-Cp)(CO)2] and [Fe(η5-Cp)(η1-Cp)- (CO)2]. For the range of complexes studied, the barriers have been successfully rationalized in terms of hyperconjugation, metal-Cp bond strength, and steric effects. In addition, the η1-η5 interconversion of the Cp binding mode is shown to be a high-energy process, consistent with experimental observations. The L substitution reactions by η1-Cp are quite sensitive to the nature of the metal center and ancillary ligand. A detailed theoretical explanation of the factors involved in all of these transformations is provided. © 2009 American Chemical Society.
Item Details
| Item Type: | Refereed Article |
|---|---|
| Research Division: | Chemical Sciences |
| Research Group: | Inorganic Chemistry |
| Research Field: | Transition Metal Chemistry |
| Objective Division: | Expanding Knowledge |
| Objective Group: | Expanding Knowledge |
| Objective Field: | Expanding Knowledge in the Chemical Sciences |
| UTAS Author: | Ariafard, A (Associate Professor Alireza Ariafard) |
| UTAS Author: | Yates, BF (Professor Brian Yates) |
| ID Code: | 62455 |
| Year Published: | 2009 |
| Funding Support: | Australian Research Council (DP0986529) |
| Web of Science® Times Cited: | 6 |
| Deposited By: | Chemistry |
| Deposited On: | 2010-03-12 |
| Last Modified: | 2010-04-12 |
| Downloads: | 0 |
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