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罕见的 Fe(IV) 烷基-亚胺迁移插入实例:Fe-C 共价键在(MeIPr)Fe(═NAd)R(R = Pe,1-降冰片)中的影响。

Rare Examples of Fe(IV) Alkyl-Imide Migratory Insertions: Impact of Fe-C Covalency in (MeIPr)Fe(═NAd)R (R = Pe, 1-nor).

机构信息

Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University , Ithaca, New York 14853, United States.

Department of Chemistry, CASCaM, University of North Texas , Denton, Texas 76201, United States.

出版信息

J Am Chem Soc. 2017 Sep 6;139(35):12145-12148. doi: 10.1021/jacs.7b06960. Epub 2017 Aug 28.

Abstract

The iron(IV) imide complexes, (MeIPr)-RFe=NAd (R = Pe (3a), 1-nor (3b)) undergo migratory insertion to iron(II) amides (MeIPr)RFe{NR(Ad)} (R = Pe (4a), 1-nor (4b)) without evidence of imidyl or free nitrene character. By increasing the field strength about iron, odd-electron reactivity was circumvented via increased covalency.

摘要

铁(IV)亚胺配合物(MeIPr)-RFe=NAd(R=Pe(3a),1-降冰片(3b))经历迁移插入到铁(II)酰胺(MeIPr)RFe{NR(Ad)}(R=Pe(4a),1-降冰片(4b))中,没有亚氨基或游离氮烯特征的证据。通过增加铁的场强,增加了共价性,从而避免了奇数电子反应性。

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