Rare Examples of Fe(IV) Alkyl-Imide Migratory Insertions: Impact of Fe-C Covalency in (Me2IPr)Fe(═NAd)R2 (R = neoPe, 1-nor)

Brian P Jacobs; Peter T Wolczanski; Quan Jiang; Thomas R Cundari; Samantha N MacMillan

doi:10.1021/jacs.7b06960

Rare Examples of Fe(IV) Alkyl-Imide Migratory Insertions: Impact of Fe-C Covalency in (Me₂IPr)Fe(═NAd)R₂ (R = ^neoPe, 1-nor)

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

Authors

Brian P Jacobs¹, Peter T Wolczanski¹, Quan Jiang², Thomas R Cundari², Samantha N MacMillan¹

Affiliations

¹ Department of Chemistry & Chemical Biology, Baker Laboratory, Cornell University , Ithaca, New York 14853, United States.
² Department of Chemistry, CASCaM, University of North Texas , Denton, Texas 76201, United States.

PMID: 28796945
DOI: 10.1021/jacs.7b06960

Abstract

The iron(IV) imide complexes, (Me₂IPr)-R₂Fe=NAd (R = ^neoPe (3a), 1-nor (3b)) undergo migratory insertion to iron(II) amides (Me₂IPr)RFe{NR(Ad)} (R = ^neoPe (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.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.