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  Electronic Structure Contributions of Non-Heme Oxo-Iron(V) Complexes to the Reactivity

Mondal, B., Neese, F., Bill, E., & Ye, S. (2018). Electronic Structure Contributions of Non-Heme Oxo-Iron(V) Complexes to the Reactivity. Journal of the American Chemical Society, 140(30), 9531-9544. doi:10.1021/jacs.8b04275.

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Mondal, Bhaskar1, Author           
Neese, Frank1, Author           
Bill, Eckhard1, Author           
Ye, Shengfa1, Author           
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1Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              

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 Abstract: Oxo-iron(V) species have been implicated in the catalytic cycle of the Rieske dioxygenase. Their synthetic analog, [FeV(O)(OC(O)CH3)(PyNMe3)]2+ (1, PyNMe3 = 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-3,6,9-trimethyl), derived from the O–O bond cleavage of its acetylperoxo iron(III) precursor, has been shown experimentally to perform regio- and stereoselective C–H and C═C bond functionalization. However, its structure–activity relation is poorly understood. Herein we present a detailed electronic-structure and spectroscopic analysis of complex 1 along with well-characterized oxo-iron(V) complexes, [FeV(O)(TAML)] (2, TAML = tetraamido macrocyclic ligand), [FeV(O)(TMC)(NC(O)CH3)]+ (4, TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), and [FeV(O)(TMC)(NC(OH)CH3)]2+ (4-H+), using wave function-based multireference complete active-space self-consistent field calculations. Our results reveal that the x/y anisotropy of the 57Fe A-matrix is not a reliable spectroscopic marker to identify oxo-iron(V) species and that the drastically different Ax and Ay values determined for complexes 1, 4, and 4-H+ have distinctive origins compared to complex 2, a genuine oxo-iron(V) species. Complex 1, in fact, has a dominant character of [FeIV(O···OC(O)CH3)2–•]2+, i.e., an SFe = 1 iron(IV) center antiferromagnetically coupled to an O–O σ* radical, where the O–O bond has not been completely broken. Complex 4 is best described as a triplet ferryl unit that strongly interacts with the trans acetylimidyl radical in an antiferromagnetic fashion, [FeIV(O)(N═C(O)CH3)]+. Complex 4-H+ features a similar electronic structure, [FeIV(O)(N═C(OH)CH3)]2+. Owing to the remaining approximate half σ-bond in the O–O moiety, complex 1 can arrange two electron-accepting orbitals (α σ*O–O and β Fe-dxz) in such a way that both orbitals can simultaneously interact with the doubly occupied electron-donating orbitals (σC–H or πC–C). Hence, complex 1 can promote a concerted yet asynchronous two-electron oxidation of the C–H and C═C bonds, which nicely explains the stereospecificity observed for complex 1 and the related species.

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Language(s): eng - English
 Dates: 2018-04-222018-07-092018-08-01
 Publication Status: Published in print
 Pages: 14
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.8b04275
 Degree: -

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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 140 (30) Sequence Number: - Start / End Page: 9531 - 9544 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870