137364-06-8Relevant academic research and scientific papers
Characterization of High Valent Iron Porphyrin in Catalytic Reaction by Iron(III) Tetrapentafluorophenylporphyrin
Fujii, Hiroshi
, p. 1491 - 1494 (1994)
High valent species formed from iron(III) meso-tetra-(pentafluorophenyl)porphyrin was first prepared in dichloromethane and characterized by low-temperature UV-vis absorption spectra, proton NMR and ESR.These measurements showed the formation of oxo iron(
First Direct Evidence for Stereospecific Olefin Epoxidation and Alkane Hydroxylation by an Oxoiron(IV) Porphyrin Complex
Nam, Wonwoo,Park, Se-Eun,Lim, In Kyung,Lim, Mi Hee,Hong, Jongki,Kim, Jinheung
, p. 14674 - 14675 (2003)
We report in this study that an oxoiron(IV) porphyrin complex bearing electron-deficient porphyrin ligand, (TPFPP)FeIV=O (TPFPP = meso-tetrakis(pentafluorophenyl)porphinato dianion), shows reactivities similar to those found in oxoiron(IV) porphyrin π-cation radicals. In the epoxidation of olefins by the (TPFPP)FeIV=O complex, epoxides were yielded as major products; cyclohexene oxide was the sole product formed in the epoxidation of cyclohexene, and stilbenes were stereospecifically oxidized to the corresponding epoxide products. More striking results were obtained in alkane hydroxylation reactions; the hydroxylation of adamantane afforded a high degree of selectivity for tertiary C?H bonds over secondary C?H bonds, and the hydroxylation of cis-1,2-dimethylcyclohexane yielded a tertiary alcohol product with >99% retention of stereochemistry. The latter result demonstrates that an oxoiron(IV) porphyrin complex hydroxylates alkanes with a high stereospecificity. Isotope labeling studies performed with H218O and 18O2 in the olefin epoxidation and alkane hydroxylation reactions demonstrated that oxygen atoms in oxygenated products derived from the oxoiron(IV) porphyrin complex. Copyright
Hydrogen Atom vs. Hydride Transfer in Cytochrome P450 Oxidations: A Combined Mass Spectrometry and Computational Study
Cantú Reinhard, Fabián G.,Fornarini, Simonetta,Crestoni, Maria Elisa,de Visser, Sam P.
, p. 1854 - 1865 (2018)
Biomimetic models of short-lived enzymatic reaction intermediates can give useful insight into the properties and coordination chemistry of transition metal complexes. In this work, we investigate a high-valent iron(IV)-oxo porphyrin cation radical complex, namely [FeIV(O)(TPFPP+·)]+, for which TPFPP is the dianion of 5,10,15,20-tetrakis(pentafluorophenyl) porphyrin. The [FeIV(O)(TPFPP+·)]+ ion was studied by ion-molecule reactions in a Fourier transform ion cyclotron resonance mass spectrometer through reactivities with 1,3,5-cycloheptatriene, 1,3-cyclohexadiene and toluene. The different substrates give dramatic changes in reaction mechanism and efficiencies, whereby cycloheptatriene leads to hydride transfer, whereas cyclohexadiene and toluene react through hydrogen atom abstraction. Detailed computational studies point to major differences in ionization energy, as well as C–H bond energies of the substrates that influence the hydrogen atom abstraction vs. electron transfer pathways. The various variables that determine the pathways for hydride transfer vs. hydrogen atom transfer are elucidated and discussed.
