title: Selectivity and mechanism of hydrogen atom transfer by an isolable imidoiron(III) complex.
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. We report a mechanistic study of HAT by an isolable iron(III) imido complex, L(Me)FeNAd (L(Me) = bulky β-diketiminate ligand, 2,4-bis(2,6-diisopropylphenylimido)pentyl; Ad = 1-adamantyl). HAT is preceded by binding of tert-butylpyridine ((t)Bupy) to form a reactive four-coordinate intermediate L(Me)Fe(NAd)((t)Bupy), 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 (t)Bupy 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.
authors.affiliation: Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
authors.forename: Ryan E
authors.initials: RE
authors.lastname: Cowley
authors.forename: Nathan A
authors.initials: NA
authors.lastname: Eckert
authors.forename: Sridhar
authors.initials: S
authors.lastname: Vaddadi
authors.forename: Travis M
authors.initials: TM
authors.lastname: Figg
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Cundari
authors.forename: Patrick L
authors.initials: PL
authors.lastname: Holland