Unprecedented Five-Coordinate Iron(IV) Imides Generate Divergent Spin States Based on the Imide R-Groups

Markus R Anneser; Gaya R Elpitiya; Jacob Townsend; Elizabeth J Johnson; Xian B Powers; Joseph F DeJesus; Konstantinos D Vogiatzis; David M Jenkins

doi:10.1002/anie.201903132

Unprecedented Five-Coordinate Iron(IV) Imides Generate Divergent Spin States Based on the Imide R-Groups

Angew Chem Int Ed Engl. 2019 Jun 11;58(24):8115-8118. doi: 10.1002/anie.201903132. Epub 2019 May 7.

Authors

Markus R Anneser¹, Gaya R Elpitiya¹, Jacob Townsend¹, Elizabeth J Johnson², Xian B Powers¹, Joseph F DeJesus¹, Konstantinos D Vogiatzis¹, David M Jenkins¹

Affiliations

¹ Department of Chemistry, University of Tennessee, Knoxville, TN, 37996, USA.
² Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, 02138, USA.

Abstract

Three five-coordinate iron(IV) imide complexes have been synthesized and characterized. These novel structures have disparate spin states on the iron as a function of the R-group attached to the imide, with alkyl groups leading to low-spin diamagnetic (S=0) complexes and an aryl group leading to an intermediate-spin (S=1) complex. The different spin states lead to significant differences in the bonding about the iron center as well as the spectroscopic properties of these complexes. Mössbauer spectroscopy confirmed that all three imide complexes are in the iron(IV) oxidation state. The combination of diamagnetism and ¹⁵ N labeling allowed for the first ¹⁵ N NMR resonance recorded on an iron imide. Multi-reference calculations corroborate the experimental structural findings and suggest how the bonding is distinctly different on the imide ligand between the two spin states.

Keywords: N-heterocyclic carbenes; imides; iron; macrocycles; organometallic chemistry.

Abstract

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