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Styrene Aziridination by Iron(IV) Nitrides
Author(s) -
Muñoz Salvador B.,
Lee WeiTsung,
Dickie Diane A.,
Scepaniak Jeremiah J.,
Subedi Deepak,
Pink Maren,
Johnson Michael D.,
Smith Jeremy M.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201503773
Subject(s) - styrene , aziridine , synthon , nitride , chemistry , metathesis , organic chemistry , polymer chemistry , polymerization , medicinal chemistry , copolymer , polymer , ring (chemistry) , layer (electronics)
Thermolysis of the iron(IV) nitride complex [PhB( t BuIm) 3 FeN] with styrene leads to formation of the high‐spin iron(II) aziridino complex [PhB( t BuIm) 3 Fe‐N(CH 2 CHPh)]. Similar aziridination occurs with both electron‐rich and electron‐poor styrenes, while bulky styrenes hinder the reaction. The aziridino complex [PhB( t BuIm) 3 Fe‐N(CH 2 CHPh)] acts as a nitride synthon, reacting with electron‐poor styrenes to generate their corresponding aziridino complexes, that is, aziridine cross‐metathesis. Reaction of [PhB( t BuIm) 3 Fe‐N(CH 2 CHPh)] with Me 3 SiCl releases the N‐functionalized aziridine Me 3 SiN(CH 2 CHPh) while simultaneously generating [PhB( t BuIm) 3 FeCl]. This closes a synthetic cycle for styrene azirdination by a nitride complex. While the less hindered iron(IV) nitride complex [PhB(MesIm) 3 FeN] reacts with styrenes below room temperature, only bulky styrenes lead to tractable aziridino products.

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