Binding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex
AuthorsAnneser, Markus R.
Högerl, Manuel P.
Kühn, Fritz E.
KAUST DepartmentKAUST Catalysis Center (KCC)
MetadataShow full item record
AbstractThe dioxygen reactivity of a cyclic iron(II) tetra–NHC-complex (NHC: N-heterocyclic carbene) is investigated. Divergent oxidation behavior is observed depending on the choice of the solvent (acetonitrile or acetone). In the first case, exposure to molecular oxygen leads to an oxygen free Fe(III) whereas in the latter case an oxide bridged Fe(III) dimer is formed. In acetone, an Fe(III)-superoxide can be trapped, isolated and characterized as intermediate at low temperatures. An Fe(III)–O–Fe(III) dimer is formed from the Fe(III) superoxide in acetone upon warming and the molecular structure has been revealed by single crystal X-ray diffraction. It is shown that the oxidation of the Fe(II) complex in both solvents is a reversible process. For the regeneration of the initial Fe(II) complex both organic and inorganic reducing agents can be used.
CitationBinding of molecular oxygen by an artificial heme analogue: investigation on the formation of an Fe–tetracarbene superoxo complex 2016 Dalton Trans.
SponsorsM. R. A. and S. H. gratefully acknowledge support by the TUM Graduate School. This project was supported through a collaboration with the King Abdullah University of Saudi-Arabia (Grant No. KSA-C0069/UKC0020).
PublisherRoyal Society of Chemistry (RSC)
Is Supplemented ByAnneser, M. R., Haslinger, S., Pöthig, A., Cokoja, M., D’Elia, V., Högerl, M. P., … Kühn, F. E. (2016). CCDC 1428063: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jy0k1
- (F(8)TPP)Fe(II)/O(2) reactivity studies [F(8)TPP = tetrakis(2,6-difluorophenyl)porphyrinate(2-)]: spectroscopic (UV-Visible and NMR) and kinetic study of solvent-dependent (Fe/O(2) = 1:1 or 2:1) reversible O(2)-reduction and ferryl formation.
- Authors: Ghiladi RA, Kretzer RM, Guzei I, Rheingold AL, Neuhold YM, Hatwell KR, Zuberbühler AD, Karlin KD
- Issue date: 2001 Nov 5
- Synthetic mononuclear nonheme iron-oxygen intermediates.
- Authors: Nam W
- Issue date: 2015 Aug 18
- Low-temperature UV-visible and NMR spectroscopic investigations of O(2) binding to ((6)L)Fe(II), a ferrous heme bearing covalently tethered axial pyridine ligands.
- Authors: Ghiladi RA, Karlin KD
- Issue date: 2002 May 6
- Fighting Fenton Chemistry: A Highly Active Iron(III) Tetracarbene Complex in Epoxidation Catalysis.
- Authors: Kück JW, Anneser MR, Hofmann B, Pöthig A, Cokoja M, Kühn FE
- Issue date: 2015 Dec 7
- Biomimetic hydrocarbon oxidation catalyzed by nonheme iron(III) complexes with peracids: evidence for an Fe(V)=O species.
- Authors: Lee SH, Han JH, Kwak H, Lee SJ, Lee EY, Kim HJ, Lee JH, Bae C, Lee SN, Kim Y, Kim C
- Issue date: 2007