title: Reactions of group 3 metals with OF2: infrared spectroscopic and theoretical investigations of the group 3 oxydifluoride OMF2 and oxyfluoride OMF molecules.
abstract: The oxidifluoride molecules, OYF(2) and OLaF(2), are produced via the reactions of laser ablated metal atoms with OF(2) in solid argon. The product structures are characterized using matrix isolation infrared spectroscopy as well as theoretical calculations. Similar to the very recently characterized OScF(2) molecule, OYF(2) is predicted to have a (2)B(2) ground state with C(2v) symmetry while the heavier OLaF(2) has a (2)A″ ground state with near C(2v) symmetry. The unpaired electron is mainly located on the terminal oxygen atom, suggesting radical character for the group 3 OMF(2) molecules. In addition, the closed shell singlet OMF molecules with bent geometries are also observed, and they are found to have triple metal-oxygen bonds with higher stretching frequencies and shorter bond lengths than their OMF(2) counterparts. α-Fluorine transfer from OF(2) to metal centers is predicted to be highly exothermic, which is very favorable for the formation of new OMF(2) and OMF species.
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904-4319, USA.
authors.forename: Yu
authors.initials: Y
authors.lastname: Gong
authors.forename: Lester
authors.initials: L
authors.lastname: Andrews
authors.forename: Charles W
authors.initials: CW
authors.lastname: Bauschlicher
mesh_terms: D005459:Fluorides / Q000737:chemistry*; D007811:Lanthanum / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared; D015019:Yttrium / Q000737:chemistry*
chemical_list: D015019:Yttrium; D007811:Lanthanum; D005459:Fluorides; D010100:Oxygen