The (POCOP)Rh fragment has been shown to catalyze C-N coupling of aryl halides and aryl amines. This is possible due to the system's ability to undergo a Rh(I)/Rh(III) transformation through the elementary steps of oxidative addition and reductive elimination; however, the specifics of the mechanism are yet to be established. Reductive elimination of the aryl amine organic product is expected to be the rate limiting step of the reaction, following concerted, first-order reductive elimination. The kinetics of C-N coupling from a Rh(III) aryl amido complex were studied under various conditions. The rate of the reaction was monitored using a fluorine-tagged aryl substituent by 19F NMR. The reductive elimination of the aryl amine product was determined to be first-order with activation parameters of ?H�= 24 +/- 1 Kcal/mol and ?S�= -9 +/- 4 eu. This research was supported by the National Science Foundation under CHE-1062840.

Kinetic studies of C-N coupling via reductive elimination from a (POCOP) supported rhodium complex

243rd National Meeting (2012)

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