作者:Salvador B. Muñoz、Wei-Tsung Lee、Diane A. Dickie、Jeremiah J. Scepaniak、Deepak Subedi、Maren Pink、Michael D. Johnson、Jeremy M. Smith
DOI:10.1002/anie.201503773
日期:2015.9.1
Thermolysis of the iron(IV) nitride complex [PhB(tBuIm)3FeN] 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
热解的铁(IV)的氮化物复合物的[值PhB(吨BuIm)3 FeN]与苯乙烯导致形成的高自旋铁(II)氮丙啶络合物[值PhB(的吨BuIm)3的Fe-N(CH 2 CHPh配合)]。富电子苯乙烯和贫电子苯乙烯都会发生类似的叠氮化,而笨重的苯乙烯会阻碍反应。叠氮基络合物[PhB(t BuIm)3 Fe-N(CH 2 CHPh)]充当氮化物合成子,与电子贫乏的苯乙烯反应生成相应的叠氮基络合物,即氮丙啶交叉复分解。[PhB(t BuIm)3 Fe-N(CH 2 CHPh)]与Me 3的反应SiCl释放N-官能化的氮丙啶Me 3 SiN(CH 2 CHPh),同时生成[PhB(t BuIm)3 FeCl]。这样就关闭了氮化物络合物进行苯乙烯叠氮化的合成循环。虽然较少受阻的铁(IV)氮化物[值PhB(MesIm)3 FeN]具有低于室温的苯乙烯反应,仅笨重苯乙烯导致易处理的氮丙啶基产物。