Abstract
With growing efforts pushing toward sustainable catalysis, using earth-abundant metals has become increasingly important. Here, we present the first examples of cobalt PC(NHC)P pincer complexes that demonstrate dual stereoselectivity for allyl ether isomerization. While the cationic cobalt complex [((PC(NHC)P)Co)(2)-μ-N(2)][BAr(4) (F)](2) (3) mainly favors the Z-isomer of the enol ether, the corresponding methyl complex [(PC(NHC)P)CoMe] (4) mostly gives the E-isomer. The dichotomy in selectivity was investigated computationally, revealing important contributions from the substituents on the metal (N(2) vs Me), including a 1,2-alkyl migration from cobalt to the N-heterocyclic carbene (NHC) of the methyl substituent, which is further explored in this report.