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Updated: Aug 22, 2026

Synthesis and Characterization of Functionalized Metal-organic Frameworks
Published on: September 5, 2014
MoF6 and WF6: nonrigid molecules?
Gustavo Santiso Quiñones1, Gerhard Hägele, Konrad Seppelt
1Freie Universität Berlin, Institut für Chemie, Anorganische und Analytische Chemie, Fabeckstrasse 34-36, 14195 Berlin, Germany.
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 CF3-CH2-O-MoF5, CF3-CH2-O-WF5, C6F5-O-MoF5, C6F5-O-WF5, and (CF3)3C-O-WF5. 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.
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