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Article Dans Une Revue Journal of the American Chemical Society Année : 2016

β-Hydride Elimination at Low-Coordinate Gold(III) Centers

Résumé

This Article reports the first comprehensive study of β-hydride elimination at gold(III). The stability/fate of gold(III) alkyl species have been investigated experimentally and computationally. A series of well-defined cationic cyclometalated gold(III) alkyl complexes [(P,C)gold(III)(R)][NTf$_2$] [(P,C) = 8-diisopropylphosphino-naphthyl; R = Me, nPr, nBu] have been synthesized and spectroscopically characterized. While the cationic gold(III) methyl derivative 3c is stable for days at room temperature, the gold(III) n-propyl and n-butyl complexes 3a,b readily undergo β-hydride elimination at low temperature to generate propylene and 2-butenes, respectively. The formation of internal olefins from the gold(III) n-butyl complex 3b shows that olefin isomerization takes place after β-hydride elimination. Computational studies indicate that this isomerization proceeds through a chain-walking mechanism involving a highly reactive gold(III) hydride intermediate and a sequence of β-hydride elimination/reinsertion into the Au-H bond. The reaction of the cationic gold(III) methyl complex 3c with ethylene was also explored. According to $^1$H and $^{13}$C NMR spectroscopy, a mixture of propylene, 1-butene, and 2-butenes is formed. DFT calculations provide detailed mechanistic insights and support the occurrence of migratory insertion of ethylene, β-hydride elimination, and olefin exchange at gold(III).
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hal-01495769 , version 1 (24-06-2024)

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Feriel Rekhroukh, Laura Estevez, Sonia Mallet-Ladeira, Karinne Miqueu, Abderrahmane Amgoune, et al.. β-Hydride Elimination at Low-Coordinate Gold(III) Centers. Journal of the American Chemical Society, 2016, 138 (36), pp.11920-11929. ⟨10.1021/jacs.6b07035⟩. ⟨hal-01495769⟩
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