MoF6 and WF6: Nonrigid Molecules?
- 4 October 2004
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 10 (19) , 4755-4762
- https://doi.org/10.1002/chem.200400095
Abstract
Calculations reveal that the octahedral–trigonal prismatic–octahedral rearrangement has particularly low‐energy barriers for MoF6, WF6, and (hypothetical) CrF6. Experimental evidence is obtained from the dynamic 19F NMR spectra of the derivatives CF3CH2OMoF5, CF3CH2OWF5, C6F5OMoF5, C6F5OWF5, and (CF3)3COWF5. The ground‐state structure of all these compounds is octahedral; at elevated temperatures the nonequivalent metal‐bound fluorine atoms undergo an intramolecular exchange. The exchange mechanism could be a 3+3 or a 2+4 twist; calculations favor the 3+3 twist.Keywords
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