title: Reaction of an iron(IV) nitrido complex with cyclohexadienes: cycloaddition and hydrogen-atom abstraction.
abstract: The iron(IV) nitrido complex PhB(MesIm)3Fe≡N reacts with 1,3-cyclohexadiene to yield the iron(II) pyrrolide complex PhB(MesIm)3Fe(η(5)-C4H4N) in high yield. The mechanism of product formation is proposed to involve sequential [4 + 1] cycloaddition and retro Diels-Alder reactions. Surprisingly, reaction with 1,4-cyclohexadiene yields the same iron-containing product, albeit in substantially lower yield. The proposed reaction mechanism, supported by electronic structure calculations, involves hydrogen-atom abstraction from 1,4-cyclohexadiene to provide the cyclohexadienyl radical. This radical is an intermediate in substrate isomerization to 1,3-cyclohexadiene, leading to formation of the pyrrolide product.
authors: Department of Chemistry, Indiana University , 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States.
authors: Wei-Tsung
authors: WT
authors: Lee
authors: Ruth A
authors: RA
authors: Juarez
authors: Jeremiah J
authors: JJ
authors: Scepaniak
authors: Salvador B
authors: SB
authors: Muñoz
authors: Diane A
authors: DA
authors: Dickie
authors: Haobin
authors: H
authors: Wang
authors: Jeremy M
authors: JM
authors: Smith
mesh_terms: D003500:Cyclization; D053138:Cyclohexenes / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D058085:Iron Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D008968:Molecular Conformation; D017672:Nitrogen Compounds / Q000737:chemistry*
chemical_list: D053138:Cyclohexenes; D058085:Iron Compounds; D017672:Nitrogen Compounds; D006859:Hydrogen