Concerted carbon-heteroatom reductive elimination is the product-forming step of many transition metal catalyzed cross-coupling reactions. We previously reported C-C reductive elimination from (POCOP)Rh as well as its ability to catalyze Kumada coupling reactions. This system has also successfully formed C-S bonds, both stoichiometrically and catalytically. (POCOP)Rh was able to catalyze the coupling of aryl-bromides and chlorides with aryl and alkyl thiols with high yields under reasonable reaction conditions. This inspired the investigation of (POCOP)Rh to perform more challenging carbon-heteroatom reductive elimination reactions such as C-F or C-O reductive elimination. Calculations from our group show the barrier of C-F reductive elimination from (POCOP)Rh(vinyl)(F) to be reasonable (?G� = 28.3 kcal/mol), however experimentally we have observed have observed C-C (POCOP) and P-F (tBuPOCOP) bond forming side reactions. We have also synthesized compounds of (tBuPOCOP)Rh(vinyl)(OR) (R = Ph or tBu) and studied their reactivity towards reductive elimination.

Exploration of carbon-heteroatom reductive elimination and catalysis from (POCOP)Rh pincer complexes

246th National Meeting (2013)

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