Reactions of Group 3 Metals with OF2: Infrared Spectroscopic and Theoretical Investigations of the Group 3 Oxydifluoride OMF2 and Oxyfluoride OMF Molecules

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• 作者：Yu Gong ; Lester Andrews ; Charles W. Bauschlicher ; Jr.
• 刊名：The Journal of Physical Chemistry A
• 出版年：2012
• 出版时间：October 18, 2012
• 年：2012
• 卷：116
• 期：41
• 页码：10115-10121
• 全文大小：261K
• 年卷期：v.116,no.41(October 18, 2012)
• ISSN：1520-5215

文摘

The oxidifluoride molecules, OYF₂ and OLaF₂, are produced via the reactions of laser ablated metal atoms with OF₂ in solid argon. The product structures are characterized using matrix isolation infrared spectroscopy as well as theoretical calculations. Similar to the very recently characterized OScF₂ molecule, OYF₂ is predicted to have a ²B₂ ground state with C_2v symmetry while the heavier OLaF₂ has a ²A鈥?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 OMF₂ molecules. In addition, the closed shell singlet OMF molecules with bent geometries are also observed, and they are found to have triple metal鈥搊xygen bonds with higher stretching frequencies and shorter bond lengths than their OMF₂ counterparts. 伪-Fluorine transfer from OF₂ to metal centers is predicted to be highly exothermic, which is very favorable for the formation of new OMF₂ and OMF species.