Perfluoroallyl chloride

An interesting recent example of a successful thermal process involves the thermal reaction of perfluoroalkyl iodides with perfluoroallyl chloride [193]. 

The reaction between perfluoroallyl chloride and Na[Mn(CO)5] leads to a white crystalline solid, m.p. 75° C, of the expected composition C3F5Mn(CO)5 38, 113). F NMR studies have shown this compound to be cT-perfluoropropenylmanganese pentacarbonyl, CF3CF=CFMn(CO)s, rather than the expected perfluoroallylmanganese pentacarbonyl, CF2= CF—CF2Mn(CO)s. 

A compound C3F5Fe(CO)2(7r-C5H5) is obtained by treating the salt 7T-C5H5Fe(CO)2Na with perfluoroallyl chloride (Section VI, B). The pattern of the F spectrum of the iron compound consists of three multiplets... 

Attempts to prepare perfluoroallyl complexes from metal carbonyl anions and perfluoroallyl chloride have been unsuccessful the perfluoroallyl rearranges and metal-o-propenyl complexes are isolated [84, 85]. However, treatment of perfluorocyclohexa ene iron tricarbonyl with caesium fluoride gives the anionic 21-perfluorocyclohexenyl complex 2.23. 

It can be seen that whereas the anion Re(CO)j causes the chlorine to leave the anion Mn(CO)j does not. Presumably the manganese anion adds to the C1FC=CF2 forming an intermediate carbanion such as (CO)sMnCF2CFCl- which subsequently abstracts a hydrogen from the solvent. With perfluoroallyl chloride, perfluoropropenyl derivatives are formed by rearrangement and loss of a chloride ion,... 

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