Polyfluoroalkyl iodides RI [I, R = Cl(CF2)4, Cl(CF2)6, CF3(CF2)3] reacted with alkenes in the presence of hydridocarbonyltris(triphenylphosphine)iridium (I) to give the corresponding adducts in excellent yields under mild conditions, I also reacted with alkynes to afford E isomer of adducts predominantly. Addition of free radical inhibitor or single electron transfer scavenger to the reaction mixture partially suppressed the reaction. Diallyl ether could be used to trap the fluoroalkyl radical to afford THF derivative XPS showed that the valence of Ir(I) increased at the end of the reaction. All findings seemed to indicate that the reaction involved a free radical chain mechanism initiated by Ir(I).

Key words: CATALYSIS, ALKYNE, ALKENE, IRIDIUM, CARBONYL COMPOUNDS, TRIPHENYLPHOSPHINE, ORGANO FLUORINE COMPOUNDS, ADDITION REACTION, FLUOROALKYLATION, FLUOROALKOXYLATION