Selectivity and Mechanism of Hydrogen Atom Transfer by an Isolable Imidoiron (III) Complex

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This article discusses a mechanistic study of hydrogen atom transfer by an isolable iron (III) imido complex, LᴹᵉFeNAd (Lᴹᵉ = bulky β-diketiminate ligand, 2,4-bis(2,6-diisopropylphenylimido)pentyl; Ad = 1-adamantyl).

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Cowley, Ryan E.; Eckert, Nathan A.; Vaddadi, Sridhar; Figg, Travis M.; Cundari, Thomas R., 1964- & Holland, Patrick L. May 12, 2011.

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This article discusses a mechanistic study of hydrogen atom transfer by an isolable iron (III) imido complex, LᴹᵉFeNAd (Lᴹᵉ = bulky β-diketiminate ligand, 2,4-bis(2,6-diisopropylphenylimido)pentyl; Ad = 1-adamantyl).

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16 p.

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Reprinted with permission from the Journal of the American Chemical Society. Copyright 2011 American Chemical Society.

Abstract: 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 by these imido complexes has a strong dependence on the size of the hydrocarbon substrate. This selectivity comes from steric hindrance by the spectator ligands, a strategy that has promise for controlling the regioselectivity of these C-H bond activation reactions.

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  • Journal of the American Chemical Society, 2011, Washington DC: American Chemical Society, pp. 9796-9811

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 133
  • Issue: 25
  • Page Start: 9796
  • Page End: 9811
  • Peer Reviewed: Yes

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  • May 12, 2011

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  • Oct. 9, 2012, 10:02 a.m.

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  • July 23, 2013, 11:36 a.m.

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Cowley, Ryan E.; Eckert, Nathan A.; Vaddadi, Sridhar; Figg, Travis M.; Cundari, Thomas R., 1964- & Holland, Patrick L. Selectivity and Mechanism of Hydrogen Atom Transfer by an Isolable Imidoiron (III) Complex, article, May 12, 2011; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc107786/: accessed September 25, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.