The Crystal Structure of a High-Spin Oxoiron(IV) Complex and Characterization of Its Self-Decay Pathway

England, Jason, Guo, Y., Farquhar, E.R. , Young Jr., V.G., Münck, E. and Que Jr., L. (2010) The Crystal Structure of a High-Spin Oxoiron(IV) Complex and Characterization of Its Self-Decay Pathway. Journal of the American Chemical Society, 132 (25). pp. 8635-8644. ISSN 0002-7863

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[FeIV(O)(TMG3tren)]2+ (1; TMG3tren = 1,1,1-tris{2-[N2-(1,1,3,3-tetramethylguanidino)]ethyl}amine) is a unique example of an isolable synthetic S = 2 oxoiron(IV) complex, which serves as a model for the high-valent oxoiron(IV) intermediates observed in nonheme iron enzymes. Congruent with DFT calculations predicting a more reactive S = 2 oxoiron(IV) center, 1 has a lifetime significantly shorter than those of related S = 1 oxoiron(IV) complexes. The self-decay of 1 exhibits strictly first-order kinetic behavior and is unaffected by solvent deuteration, suggesting an intramolecular process. This hypothesis was supported by ESI-MS analysis of the iron products and a significant retardation of self-decay upon use of a perdeuteromethyl TMG3tren isotopomer, d36-1 (KIE = 24 at 25 °C). The greatly enhanced thermal stability of d36-1 allowed growth of diffraction quality crystals for which a high-resolution crystal structure was obtained. This structure showed an Fe═O unit (r = 1.661(2) Å) in the intended trigonal bipyramidal geometry enforced by the sterically bulky tetramethylguanidinyl donors of the tetradentate tripodal TMG3tren ligand. The close proximity of the methyl substituents to the oxoiron unit yielded three symmetrically oriented short C−D···O nonbonded contacts (2.38−2.49 Å), an arrangement that facilitated self-decay by rate-determining intramolecular hydrogen atom abstraction and subsequent formation of a ligand-hydroxylated iron(III) product. EPR and Mössbauer quantification of the various iron products, referenced against those obtained from reaction of 1 with 1,4-cyclohexadiene, allowed formulation of a detailed mechanism for the self-decay process. The solution of this first crystal structure of a high-spin (S = 2) oxoiron(IV) center represents a fundamental step on the path toward a full understanding of these pivotal biological intermediates.

Keywords:Close proximity, Cyclohexadienes, Decay process, Deuterations, DFT calculation, First order kinetics, High resolution crystal structure, Intramolecular hydrogen, Intramolecular process, Non-heme iron enzymes, Oxoiron, Quality crystals, Tetradentate, Thermal stability, Trigonal bipyramidal geometry, Decay (organic), Deuterium, Iron compounds, Ligands, Spin dynamics, Thermodynamic stability, Crystal structure, iron complex, oxoiron complex, unclassified drug, organometallic compound, article, chemical structure, crystal structure, density functional theory, electrospray, mass spectrometry, thermostability, chemistry, conformation, kinetics, quantum theory, spectroscopy, X ray crystallography, Crystallography, X-Ray, Models, Molecular, Molecular Conformation, Organometallic Compounds, Spectrum Analysis, Crystallography, X-Ray, Spectrum Analysis
Subjects:F Physical Sciences > F120 Inorganic Chemistry
Divisions:College of Science > School of Chemistry
ID Code:51925
Deposited On:14 Oct 2022 14:40

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