Salvador B Muñoz1, Wei-Tsung Lee1, Diane A Dickie2, Jeremiah J Scepaniak3, Deepak Subedi3, Maren Pink1, Michael D Johnson3, Jeremy M Smith4. 1. Department of Chemistry, Indiana University, 800 E. Kirkwood Avenue, Bloomington, IN 47403 (USA). 2. Department of Chemistry and Chemical Biology, The University of New Mexico, Albuquerque, NM 87131 (USA). 3. Department of Chemistry and Biochemistry, New Mexico State University, Las Cruces, NM 88003 (USA). 4. Department of Chemistry, Indiana University, 800 E. Kirkwood Avenue, Bloomington, IN 47403 (USA). smith962@indiana.edu.
Abstract
Thermolysis of the iron(IV) nitride complex [PhB(tBuIm)3Fe≡N] with styrene leads to formation of the high-spin iron(II) aziridino complex [PhB(tBuIm)3Fe-N(CH2CHPh)]. Similar aziridination occurs with both electron-rich and electron-poor styrenes, while bulky styrenes hinder the reaction. The aziridino complex [PhB(tBuIm)3Fe-N(CH2CHPh)] acts as a nitride synthon, reacting with electron-poor styrenes to generate their corresponding aziridino complexes, that is, aziridine cross-metathesis. Reaction of [PhB(tBuIm)3Fe-N(CH2CHPh)] with Me3SiCl releases the N-functionalized aziridine Me3SiN(CH2CHPh) while simultaneously generating [PhB(tBuIm)3FeCl]. This closes a synthetic cycle for styrene azirdination by a nitride complex. While the less hindered iron(IV) nitride complex [PhB(MesIm)3Fe≡N] reacts with styrenes below room temperature, only bulky styrenes lead to tractable aziridino products.
Thermolysis of the iron(IV) nitride complex [PhB(n class="Chemical">tBuIm)3Fe≡N] with styrene leads to formation of the high-spin iron(II) aziridino complex [PhB(tBuIm)3Fe-N(CH2CHPh)]. Similar aziridination occurs with both electron-rich and electron-poor styrenes, while bulky styrenes hinder the reaction. The aziridino complex [PhB(tBuIm)3Fe-N(CH2CHPh)] acts as a nitride synthon, reacting with electron-poor styrenes to generate their corresponding aziridino complexes, that is, aziridine cross-metathesis. Reaction of [PhB(tBuIm)3Fe-N(CH2CHPh)] with Me3SiCl releases the N-functionalized aziridine Me3SiN(CH2CHPh) while simultaneously generating [PhB(tBuIm)3FeCl]. This closes a synthetic cycle for styrene azirdination by a nitride complex. While the less hindered iron(IV) nitride complex [PhB(MesIm)3Fe≡N] reacts with styrenes below room temperature, only bulky styrenes lead to tractable aziridino products.
Authors: M D Timken; C E Strouse; S M Soltis; S A Daverio; D N Hendrickson; A M Abdel-Mawgoud; S R Wilson Journal: J Am Chem Soc Date: 1986-02-01 Impact factor: 15.419
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