Catalysts for radical addition

Copper(I) salts have been found to be particularly good catalysts for radical addition of alkyl halides to alkenes689. These catalysts have been used in the reaction of carbon tetrachloride with ester-containing alkenes, the products being key intermediates in the synthesis of -lactams (equation 108). 

Photoexcited Ti02 can work as a catalyst for radical addition of tertiary amines to electron deficient alkenes. In particular, A-methylpyrrolidine containing a. 

Dimolybdenum quadraple bonds can also act as catalysts for radical addition and polymerisation reactions. Their performance can be tuned by modifying the redox potential of the dimetal core. For example, the carbo)grlate bridged compound Mo2(TiPB)4 ( 4/2 = 0.140 V vs. Fc/Fc ) acts as a catalyst for radical addition reactions of polyhaloalkanes to 1-alkenes and cyclopentene, while the formamidinate and guanidi-nate bridged compounds ( 1/2 = —0.308 V and —0.581 V, respectively) are effective catalysts for the radical polymerisation of methyl methacrylate. 

O for S substitution [22], This large change in redox potential can alter the reactivity of the MOj core the dimolybdenum tetracarboxylate Mo2(T PB)4 can act as a catalyst for radical addition reactions of polyhaloalkanes to 1-alkenes, whereas amidinate and guanidinate analogs are catalysts for the radical polymerization of methyl methacrylate [23]. 

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