Competitive gold/nickel transmetalation

Demchuk, Mitchell J. and Zurakowski, Joseph A. and Austen, Brady J. H. and Nelson, David J. and Drover, Marcus W. (2021) Competitive gold/nickel transmetalation. Chemical Communications, 58 (1). pp. 68-71. ISSN 1359-7345 (

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Transmetalation is a key method for the construction of element–element bonds. Here, we disclose the reactivity of [NiII(Ar)(I)(diphosphine)] compounds with arylgold(I) transmetalating agents, which is directly relevant to cross-coupling catalysis. Both aryl-for-iodide and unexpected aryl-for-aryl transmetalation are witnessed. Despite the strong driving force expected for Au–I bond formation, aryl scrambling can occur during transmetalation and may complicate the outcomes of attempted catalytic cross-coupling reactions.