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Infrared Spectroscopic and Theoretical Studies on the OMF 2 and OMF (M = Cr, Mo, W) Molecules in Solid Argon.
Journal of Physical Chemistry. A 2017 October 13
Group 6 metal oxide fluoride molecules in the form of OMF2 and OMF (M = Cr, Mo, W) were prepared via the reactions of laser-ablated metal atoms and OF2 in excess argon. Product identifications were performed by using infrared spectroscopy,18 OF2 samples, and electronic structure calculations. Reactions of group 6 metal atoms and OF2 resulted in the formation of ternary OCrF2 , OMoF2 , and OWF2 molecules with C2v symmetry in which the tetravalent metal center is coordinated by one oxygen and two fluorine atoms. Both OCrF2 and OMoF2 are computed to possess triplet ground states, and a closed shell singlet is the ground state for OWF2 . Triatomic OCrF, OMoF, and OWF molecules were also observed during sample deposition. All three molecules were computed to have a bent geometry and quartet ground state. A bonding analysis showed that the OMF2 molecules have highly ionic M-F bonds.3 OCrF2 and3 OMoF2 have an M-O double bond composed of a σ bond and a π bond.1 OWF2 has an M-O triple bond consisting of a σ bond, a π bond, and a highly delocalized O lone pair forming the other π bond. The M-O bonds in the OMF compounds have triple-bond character for all three metals.
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