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Mechanistic Studies of Ligand Fluxionality in [Mo(5-Cp)(1-Cp)(L)2]n


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]

DOI: doi:10.1021/jp810032a


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:7
Deposited By:Chemistry
Deposited On:2010-03-12
Last Modified:2010-04-12

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