Insertion reactions fluoro-olefins

Free-radical Reactions.—number of further publications have appeared concerning the free-radical insertion of fluoro-olefins into C—H bonds (see Voi. 2, p. 122). Perokide-initiated reaction of toluene, and other alkyl benzenes having benzylic hydrogens, with hexafluoropropene yields mainly the adduct (89) and some of the indane (90) arising from cyclization of the initially formed radical, with subsequent dehydrogenation. The indane (90) yields the corresponding indene with ethanolic... 

Other alkenyl complexes have been formed by displacement of fluoride or chloride ion from fluoro-olefins by metal carbonyl anions, by reactions of the perfluoroalkenylsilver derivative with metal halide compounds, and by insertion of an alkyne into a metal-X bond, and parameters are given with structures [168] to [187]. (8, 86-91) As... 

Photochemical reactions of Me3M-Mn(CO)6 (M = Si or Ge) with fluoro-olefins and acetylenes give low yields of products resulting from insertion into the M—Mn bond or, presumably, from decomposition of such products (see also p. 201), e.g. 

The reaction of terminal fluoro olefins with SO3 at low temperatures affords the [2+2] cycloadducts in good yields. Examples of this type of reaction are listed in Table 7.4. However, insertion of sulfur trioxide into allylic C-F bonds often occurs simultaneously . ... 

Fluoro-olefins may react in three ways with complexes of nickel, palladium, and platinum (i) halogen (or pseudo-halogen) transfer to the metal may occur with formation of a vinyl derivative (ii) the olefin monoadduct may be stable [these are probably best regarded as metal(n) complexes] or (iii) insertion of a further mole of olefin may occur, a metallo-cyclopentane being formed. The possible reaction pathway is affected by quite subtle changes in the olefin and in the metal ligands. 

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