Preparations and Reactions of Inorganic Main-Group Oxide Fluorides

Abstract

This chapter discusses the preparations and reactions of inorganic main-group oxide fluorides. It summarizes the preparations and chemical properties of the presently known oxide fluorides of the main-group elements. The replacement of fluorine atoms with oxygen atoms tends to stabilize higher oxidation states. For example, ClO 3 F, C1O 2 F 3 , XeO 3 F 2 , and XeO 2 F 4 exhibit the oxidation states Cl(VII) and Xe(VIII), whereas the highest oxidation state binary fluorides yield only Cl(V) in ClF 5 and Xe(V1) in XeF6. The simplest oxide fluoride of phosphorus is phosphoryl fluoride, POF 3 , which exists as a colorless gas. It is generally prepared by fluorination of phosphoryl chloride with metallic fluorides such as lead, zinc, silver, or sodium fluoride, but can also be prepared directly by reaction of MgF 2 and Mg 2 P 2 O 7 above 750°C and, together with P 2 O 3 F 4 , from the reaction of PF 5 , O 2 , and Mg at 300°C.