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π-Complexation in Nickel-Catalyzed Cross-Coupling Reactions
- Sontag, S. Kyle, Bilbrey, Jenna
A., Huddleston, N. Eric, Sheppard, Gareth R., Allen, Wesley D., Locklin, Jason
- Journal of organic chemistry 2014 v.79 no.4 pp. 1836-1841
- catalysts, chemical structure, cross-coupling reactions, isotopes, methodology, nickel, organic chemistry, thiophene
- The kinetic isotope effect (KIE) is used to experimentally elucidate the first irreversible step in oxidative addition reactions of a zerovalent nickel catalyst to a set of haloarene substrates. Halogenated o-methylbenzene, dimethoxybenzene, and thiophene derivatives undergo intramolecular oxidative addition through irreversible π-complexation. Density functional theory computations at the B3LYP-D3/TZ2P-LANL2TZ(f)-LANL08d level predict η²-bound π-complexes are generally stable relative to a solvated catalyst plus free substrate and that ring-walking of the Ni(0) catalyst and intramolecular oxidative addition are facile in these intermediates.