In nickel-mediated Kumada cross-coupling reactions, low valent active nickel complexes are often generated in situ and the ligands usually govern the reactivity or stability of these complexes. However, the decomposition of active nickel complexes is inevitable if the subsequent reaction is sluggish. While we recently developed AgF-assisted nickel catalysis to cross-couple methyl ethers and silylmagnesium reagents, the intriguing catalytic role of AgF and the actual active nickel species remains elusive. Recently, both Ni(0) and Ni(I) intermediate complexes are identified as active species in Kumada cross-coupling reactions. Control experiments in combination with 31P nuclear magnetic resonance (NMR) suggest that AgF attenuates the decomposition of in situ generated Ni(0) species. The plausible Ni(0) and Ni(I) intermediate complexes were synthesized, and experimental findings are consistent with the actual catalytic cycle being Ni(0)/Ni(II) rather than Ni(I)/Ni(III).
Venkadesh Balakrishnan, Vetrivelan Murugesan, Bincy Chindan, and Ramesh Rasappan* Attenuation of Ni (0) decomposition: Mechanistic insights into AgF-assisted nickel-mediated silylation. Inorganic Chemistry, 61(3), 1438-1446.