Date: May 12, 2011
Creator: Cowley, Ryan E.; Eckert, Nathan A.; Vaddadi, Sridhar; Figg, Travis M.; Cundari, Thomas R., 1964- & Holland, Patrick L.
Description: This article discusses the selectivity and mechanism of hydrogen atom transfer by an isolable imidoiron (III) complex. In the literature, iron-oxo complexes have been isolated and their hydrogen atom transfer (HAT) reactions have been studied in detail. Iron-imido complexes have been isolated more recently, and the community needs experimental evaluations of the mechanism of HAT from late-metal imido species. The authors report a mechanistic study of HAT by an isolable iron (III) imido complex, LᴹᵉFeNAd (Lᴹᵉ = bulky β-diketiminate ligand, 2,4-bis(2,6-diisopropylphenylimido)pentyl; Ad = 1-adamantyl). HAT is preceded by binding of tert-butylpyridine (ᵗBupy) to form a reactive four-coordinate intermediate LᴹᵉFe(NAd)(ᵗBupy), as shown by equilibrium and kinetic studies. In the HAT step, very large substrate H/D kinetic isotope effects around 100 are consistent with C-H bond cleavage. The elementary HAT rate constant is increased by electron-donating groups on the pyridine additive, and by a more polar medium. When combined with the faster rate of HAT from indene versus cyclohexadiene, this trend is consistent with H⁺ transfer character in the HAT transition state. The increase in HAT rate in the presence of ᵗBupy may be explained by a combination of electronic (weaker Fe=N π-bonding) and thermodynamic (more exothermic HAT) effects. Most importantly, HAT ...
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