Extending the Row of Lanthanide Tetrafluorides: A Combined Matrixâ Isolation and Quantumâ Chemical Study

Only the neutral tetrafluorides of Ce, Pr, and Tb as well as the [LnF7]3â anions of Dy and Nd, with the metal in the +IV oxidation state, have been previously reported. We report our attempts to extend the row of neutral lanthanide tetrafluorides through the reaction of laserâ ablated metal atoms with fluorine and their stabilization and characterization by matrixâ isolation IR spectroscopy. In addition to the above three tetrafluorides, we found two new tetrafluorides, 3NdF4 and 7DyF4, both of which are in the +IV oxidation state, which extends this lanthanide oxidation state to two new metals. Our experimental results are supported by quantumâ chemical calculations and the role of the lanthanide oxidation state is discussed for both the LnF4 and [LnF4]â species. Most of the LnF4 species are predicted to be in the +IV oxidation state and all of the [LnF4]â anions are predicted to be in the +III oxidation state. The LnF4 species are predicted to be strong oxidizing agents and the LnF3 species are predicted to be moderate to strong Lewis acids.Lanthanide tetrafluorides extended: Two new tetrafluorides, 3NdF4 and 7DyF4, both of which are in the +IV oxidation state, are reported; these compounds extend the examples of neutral lanthanide tetrafluorides beyond those of Ce, Pr, and Tb. The new compounds were formed by reaction of laserâ ablated metal atoms with fluorine and their stabilization and characterization by matrixâ isolation IR spectroscopy are supported by quantumâ chemical calculations (see figure).Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/137267/1/chem201504182.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/137267/2/chem201504182-sup-0001-misc_information.pd