The Crystal Structure of a High-Spin Oxoiron(IV) Complex and Characterization of Its Self-Decay Pathway
[Fe{sup IV}(O)(TMG{sub 3}tren)]{sup 2+} (1; TMG{sub 3}tren = 1,1,1-tris{l_brace}2-[N{sup 2}-(1,1,3,3-tetramethylguanidino)]ethyl{r_brace}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 TMG{sub 3}tren isotopomer, d{sub 36}-1 (KIE = 24 at 25 C). The greatly enhanced thermal stability of d{sub 36}-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) {angstrom}) in the intended trigonal bipyramidal geometry enforced by the sterically bulky tetramethylguanidinyl donors of the tetradentate tripodal TMG{sub 3}tren ligand. The close proximity of the methyl substituents to the oxoiron unit yielded three symmetrically oriented short C-D {hor_ellipsis} O nonbonded contacts (2.38-2.49 {angstrom}), 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 Moessbauer 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.
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source
- Sponsoring Organization:
- DOE - OFFICE OF SCIENCE
- DOE Contract Number:
- DE-AC02-98CH10886
- OSTI ID:
- 1019834
- Report Number(s):
- BNL-95680-2011-JA; JACSAT; TRN: US201115%%470
- Journal Information:
- Journal of the American Chemical Society, Vol. 132, Issue 25; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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