0000000001315458
AUTHOR
Williamson N. Oloo
Trapping a Highly Reactive Nonheme Iron Intermediate That Oxygenates Strong C—H Bonds with Stereoretention
An unprecedentedly reactive iron species (2) has been generated by reaction of excess peracetic acid with a mononuclear iron complex [FeII(CF3SO3)2(PyNMe3)] (1) at cryogenic temperatures, and characterized spectroscopically. Compound 2 is kinetically competent for breaking strong C-H bonds of alkanes (BDE ≈ 100 kcal·mol-1) through a hydrogen-atom transfer mechanism, and the transformations proceed with stereoretention and regioselectively, responding to bond strength, as well as to steric and polar effects. Bimolecular reaction rates are at least an order of magnitude faster than those of the most reactive synthetic high-valent nonheme oxoiron species described to date. EPR studies in tande…
Spectroscopic and DFT Characterization of a Highly Reactive Nonheme FeV–Oxo Intermediate
The reaction of [(PyNMe3)FeII(CF3SO3)2], 1, with excess peracetic acid at −40 °C generates a highly reactive intermediate, 2b(PAA), that has the fastest rate to date for oxidizing cyclohexane by a nonheme iron species. It exhibits an intense 490 nm chromophore associated with an S = 1/2 EPR signal having g-values at 2.07, 2.01, and 1.94. This species was shown to be in a fast equilibrium with a second S = 1/2 species, 2a(PAA), assigned to a low-spin acylperoxoiron(III) center. Unfortunately, contaminants accompanying the 2(PAA) samples prevented determination of the iron oxidation state by Mossbauer spectroscopy. Use of MeO-PyNMe3 (an electron-enriched version of PyNMe3) and cyclohexyl pero…
CCDC 1840192: Experimental Crystal Structure Determination
Related Article: Ruixi Fan, Joan Serrano-Plana, Williamson N. Oloo, Apparao Draksharapu, Estefanía Delgado-Pinar, Anna Company, Vlad Martin-Diaconescu, Margarida Borrell, Julio Lloret-Fillol, Enrique García-España, Yisong Guo, Emile L. Bominaar, Lawrence Que Junior, Miquel Costas, Eckard Münck|2018|J.Am.Chem.Soc.|140|3916|doi:10.1021/jacs.7b11400
CCDC 1036385: Experimental Crystal Structure Determination
Related Article: Joan Serrano-Plana, Williamson N. Oloo, Laura Acosta-Rueda, Katlyn K. Meier, Begoña Verdejo, Enrique García-España, Manuel G. Basallote, Eckard Münck, Lawrence Que Junior, Anna Company, and Miquel Costas|2015|J.Am.Chem.Soc.|137|15833|doi:10.1021/jacs.5b09904
CCDC 1446018: Experimental Crystal Structure Determination
Related Article: Joan Serrano-Plana, Williamson N. Oloo, Laura Acosta-Rueda, Katlyn K. Meier, Begoña Verdejo, Enrique García-España, Manuel G. Basallote, Eckard Münck, Lawrence Que Junior, Anna Company, and Miquel Costas|2015|J.Am.Chem.Soc.|137|15833|doi:10.1021/jacs.5b09904