Journal ArticleDOI
Oxidation of C-H bonds by [(bpy)2(py)RuIVO]2+ occurs by hydrogen atom abstraction.
Jasmine R. Bryant,James M. Mayer +1 more
TLDR
The data indicate a mechanism of initial hydrogen-atom abstraction forming radicals that dimerize, disproportionate and are trapped by the oxidant, which appears to apply to the oxidations of toluene, ethylbenzene, cumene, indene, and cyclohexene.Abstract:
Anaerobic oxidations of 9,10-dihydroanthracene (DHA), xanthene, and fluorene by [(bpy)2(py)RuIVO]2+ in acetonitrile solution give mixtures of products including oxygenated and non-oxygenated compounds. The products include those formed by organic radical dimerization, such as 9,9‘-bixanthene, as well as by oxygen-atom transfer (e.g., xanthone). The kinetics of these reactions have been measured. The kinetic isotope effect for oxidation of DHA vs DHA-d4 gives kH/kD ≥ 35 ± 1. The data indicate a mechanism of initial hydrogen-atom abstraction forming radicals that dimerize, disproportionate and are trapped by the oxidant. This mechanism also appears to apply to the oxidations of toluene, ethylbenzene, cumene, indene, and cyclohexene. The rate constants for H-atom abstraction from these substrates correlate well with the strength of the C−H bond that is cleaved. Rate constants for abstraction from DHA and toluene also correlate with those for oxygen radicals and other oxidants. The rate constant for H-atom tr...read more
Citations
More filters
Journal ArticleDOI
Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications
TL;DR: This issue discusses proton-coupled electron transfer or PCET processes, which are central to a great many chemical and biochemical processes, from biological catalysis and energy transduction, to bulk industrial chemical processes, to new approaches to solar energy conversion.
Journal ArticleDOI
Proton-coupled electron transfer: a reaction chemist's view.
TL;DR: Intrinsic barriers for PCET can be comparable to or larger than those for ET, and many PCET/HAT rate constants are predicted well by the Marcus cross relation.
Journal ArticleDOI
Understanding Hydrogen Atom Transfer: From Bond Strengths to Marcus Theory
TL;DR: The development of a conceptual framework for HAT with a Marcus theory approach is described, which shows that the Marcus approach based on free energies and intrinsic barriers captures much of the essential chemistry of HAT reactions.
Journal ArticleDOI
Nonheme FeIVO complexes that can oxidize the C-H bonds of cyclohexane at room temperature.
József Kaizer,Eric J. Klinker,Na Young Oh,Jan Uwe Rohde,Woon Ju Song,Audria Stubna,Jinheung Kim,Eckard Münck,Wonwoo Nam,Lawrence Que +9 more
TL;DR: Nonheme oxoiron(IV) complexes of two pentadentate ligands have been generated and found to have spectroscopic properties similar to the closely related tetradentate TPA (tris(2-pyridylmethyl)amine) complex reported earlier.
Journal ArticleDOI
C-H bond activations by metal oxo compounds.
Ahmet Gunay,Klaus H. Theopold +1 more
TL;DR: In an era dominated by the utilization of hydrocarbon mixtures as feedstocks for the chemical industry, the functionalization of C-H bonds, particularly in a selective manner, remains one of the most fundamental problems of chemistry.
References
More filters
Journal ArticleDOI
Equilibrium Acidities in Dimethyl Sulfoxide Solution
TL;DR: The first acidity scale to be established in a pure solvent other than water was the result of the pioneering work of Conant, Wheland, and McEwen in ether or ben~ene.
Journal ArticleDOI
Hydrogen atom abstraction by metal-oxo complexes : understanding the analogy with organic radical reactions
Journal ArticleDOI
Which Factors Determine the Reactivity and Regioselectivity of Free Radical Substitution and Addition Reactions
TL;DR: In this paper, the relative importance of bond strength, steric effects, and polarity in determining the rate and orientation of free radical subsitution and free radical addition reaction is considered.
Journal ArticleDOI
Structural and solvent effects evaluated from acidities measured in dimethyl sulfoxide and in the gas phase
TL;DR: In this paper, it was concluded that the SN2 reactions of 9-R2N-Flions with Ph2CHCl are occurring by a radical pair mechanism, which can be of general use for elucidating the role of SET in reactions of families of anions with electrophiles.
Journal ArticleDOI
The Elusive Oxidant Species of Cytochrome P450 Enzymes: Characterization by Combined Quantum Mechanical/Molecular Mechanical (QM/MM) Calculations
Jan Schöneboom,Hai Lin,Nathalie Reuter,Walter Thiel,Shimrit Cohen,François Ogliaro,Sason Shaik +6 more
TL;DR: Combined quantum mechanical/molecular mechanical (QM/MM) calculations of Compound I of cytochrome P450(cam) in the full enzyme environment as well as density functional studies of the isolated QM region show that the protein environment and its specific hydrogen bonding to the cysteinate ligand are crucial for sustaining the Fe-S bond and for preventing the full oxidation of the sulfur.