Fluoroformic Acid Anhydride, FC(O)OC(O)F

HOLGER PERNICE; HELGE WILLNER; KARINA BIERBRAUER; MAXIMILIANO BURGOS PACI; GUSTAVO A. ARGÜELLO

Angewandte Chemie

Wiley-VCH

Lugar: Weinheim; Año: 2002 vol. 41 p. 3832 - 3834

1433-7851

  For many years new molecules, consisting only of fluorine,carbon, and oxygen atoms have been of fundamental inter-est.[1±10] The view that such species are formed in atmosphericdegradation of HFCs and other CFC replacements[11, 12] hasmotivated further work in this field.[13±16]   During our studies on radicals such as CF3O,[17] CF3OO,[18]CF3OC(O),[19] FCO2[20] , and FC(O)OO[18] that are importantintermediates in the atmospheric degradation of CFC replace-ments, as well as on the catalytic oxidation of CO by CF3Oxradicals,[21, 22] we have also considered possible reactionproducts of these radicals, among them CF3OC(O)OO-C(O)OCF3.[17] Correspondingly, the formation of fluorofor-mic acid anhydride, FC(O)OC(O)F (1), by a recombination ofFCO and FCO2 radicals is considered in principle as feasible.However both radicals have to be present in sufficiently highconcentrations for a satisfactory yield. We now report on thesynthesis and characterization of 1. This fundamental acidanhydride is, to our knowledge the first example of aXC(O)OC(O)Y species, with X,Y 1⁄4 halogen and can beviewed as halogen dicarbonate. It is at the same time thelast missing member in the family of FC(O)OxC(O)Fmolecules (x 1⁄4 0,[23] 1 (this work), 2,[1] 3,[24] ), which had notpreviously been isolated in pure form.