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Abstract We report the synthesis and spectroscopic characterization of a series of iron‐carbene complexes in redox states {Fe=C(H)Ar}10–11. Pulse EPR studies of the1,2H and13C isotopologues of {Fe=C(H)Ar}11reveal the high covalency of the Fe–carbene bonding, leading to a more even spin distribution than commonly observed for reduced Fischer carbenes.
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Unprecedented Five‐Coordinate Iron(IV) Imides Generate Divergent Spin States Based on the Imide R‐Groups
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 and15N labeling allowed for the first15N 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.
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- Award ID(s):
- 1800237
- PAR ID:
- 10102897
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie
- Volume:
- 131
- Issue:
- 24
- ISSN:
- 0044-8249
- Page Range / eLocation ID:
- p. 8199-8202
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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