Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 17, Issue 5, Pages 1622-1634Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201002297
Keywords
bioinorganic chemistry; iron; oxygenases; reaction mechanisms; tetradentate ligands
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Funding
- MEC-Spain [CTQ2009-08464/BQU, CTQ2008-06696/BQU]
- US National Institutes of Health [GM-33162, EB-001475]
- Generalitat de Catalunya [SGR 2009 SGR 637]
- MEC
- NATIONAL INSTITUTE OF BIOMEDICAL IMAGING AND BIOENGINEERING [R01EB001475] Funding Source: NIH RePORTER
- NATIONAL INSTITUTE OF GENERAL MEDICAL SCIENCES [R01GM033162, R37GM033162] Funding Source: NIH RePORTER
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The spectroscopic and chemical characterization of a new synthetic non-heme iron(IV)-oxo species [Fe-IV(O)((Me,H)Pytacn)(S)](2+) (2, (Me,H)Pytacn=1-(2'-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane, S=CH3CN or H2O) is described. Complex 2 was prepared by reaction of [Fe-II-(CF3SO3)(2)((Me,H)Pytacn)] (1) with peracetic acid. Complex 2 bears a tetradentate N-4 ligand that leaves two cis sites available for binding an oxo group and a second external ligand but, unlike the related iron(IV)-oxo species with tetradentate ligands, it is remarkably stable at room temperature (t(1/2) > 2h at 288 K). Its ability to exchange the oxygen atom of the oxo ligand with water has been analyzed in detail by means of kinetic studies, and a mechanism is proposed on the basis of DFT calculations. Hydrogen-atom abstraction from C-H bonds and oxygen-atom transfer to sulfides by 2 have also been studied. Despite its thermal stability, 2 proves to be a very powerful oxidant that is capable of breaking the strong C-H bond of cyclohexane (bond dissociation energy =99.3 kcal mol(-1)).
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