Selectivity and mechanism of hydrogen atom transfer by an isolable imidoiron(III) complex

J Am Chem Soc. 2011 Jun 29;133(25):9796-811. doi: 10.1021/ja2005303. Epub 2011 Jun 8.

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.