Diane Dickie - Reaction of an Iron(IV) Nitrido Complex with Cyclohexadienes: Cycloaddition and Hydrogen-Atom Abstraction.

Document created by Diane Dickie on Nov 17, 2015
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  Publication Details (including relevant citation   information):

  Lee, Wei-Tsung, Juarez, Ruth A., Scepaniak, Jeremiah J., Munoz,   Salvador B., Dickie, Diane A., Wang, Haobin, Smith, Jeremy M.   Inorganic Chemistry 53 (16) 8425-8430

  Abstract: The Fe(IV) nitrido complex   PhB(MesIm)3Fe≡N reacts with 1,3-cyclohexadiene to yield the   Fe(II) pyrrolide complex PhB(MesIm)3Fe(η5-C4H4N) in high yield.   The mechanism of product formation is proposed to involve   sequential [4 + 1] cycloaddn. and retro Diels-Alder reactions.   Surprisingly, reaction with 1,4-cyclohexadiene yields the same   Fe-contg. product, albeit in substantially lower yield. The   proposed reaction mechanism, supported by electronic structure   calcns., involves H-atom abstraction from 1,4-cyclohexadiene to   provide the cyclohexadienyl radical. This radical is an   intermediate in substrate isomerization to 1,3-cyclohexadiene,   giving the pyrrolide product. [on SciFinder(R)]

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