Oxidation of C-H bonds by [(bpy)2(py)RuIVO]2+ occurs by hydrogen atom abstraction

Anaerobic oxidations of 9,10-dihydroanthracene (DHA), xanthene, and fluorene by [(bpy)(2)(py)Ru(IV)O](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-d(4) gives k(H)/k(D) > or = 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 transfer from toluene to [(bpy)(2)(py)Ru(IV)O](2+) appears to be close to that predicted by the Marcus cross relation, using a tentative rate constant for hydrogen atom self-exchange between [(bpy)(2)(py)Ru(III)OH](2+) and [(bpy)(2)(py)Ru(IV)O](2+).     

Diffusion controlled hydrogen atom abstraction from tertiary amines by the benzyloxyl radical. The importance of C-H/N hydrogen bonding

The rate constants for H-atom abstraction (k(H)) from 1,4-cyclohexadiene (CHD), triethylamine (TEA), triisobutylamine (TIBA), and DABCO by the cumyloxyl (CumO(?)) and benzyloxyl (BnO(?)) radicals were measured. Comparable k(H) values for the two radicals were obtained in their reactions with CHD and TIBA whereas large increases in k(H) for TEA and DABCO were found on going from CumO(?) to BnO(?). These differences are attributed to the rate-determining formation of BnO(?) C-H/amine N lone-pair H-bonded complexes.     

Copper-catalyzed amidation of sp3 C-H bonds adjacent to a nitrogen atom

We have developed a novel copper-catalyzed amidation of unactivated sp(3) C-H bonds adjacent to a nitrogen atom by using an inexpensive catalyst-oxidant (CuBr/(t)BuOOH) system under mild conditions. The dephenylation was first found for N-benzylaniline, and the new class of products provide diverse structures for pharmaceuticals and combinatorial chemistry.     

*H atom and *OH radical reactions with 5-methylcytosine

The reactions between either a hydrogen atom or a hydroxyl radical and 5-methylcytosine (5-MeCyt) are studied by using the hybrid kinetic energy meta-GGA functional MPW1B95. *H atom and *OH radical addition to positions C5 and C6 of 5-MeCyt, or *OH radical induced H-abstraction from the C5 methyl group, are explored. All systems are optimized in bulk solvent. The data presented show that the barriers to reaction are very low: ca. 7 kcal/mol for the *H atom additions and 1 kcal/mol for the reactions involving the *OH radical. Thermodynamically, the two C6 radical adducts and the *H-abstraction product are the most stable ones. The proton hyperfine coupling constants (HFCC), computed at the IEFPCM/MPW1B95/6-311++G(2d,2p) level, agree well with B3LYP results and available experimental and theoretical data on related thymine and cytosine radicals.     

Free radical abstraction of H atom from peroxides with concerted dissociation of O-O bond

Quantum chemical calculations of the dissociation energy of the C-H bond in the ??-hydroperoxide fragment of Me₂CHOOH were carried out. It was shown that abstraction of H atom is accompanied by dissociation of the O-O bond. Density functional calculations of transition states of the reactions of ^·CH₃, CH₃OO^·, and HO₂ ^· radicals with the C-H bond in the ??-hydroperoxide fragment of Me₂CHOOH were carried out. It was established that H atom abstraction is accompanied by concerted dissociation of the O-O bond. For 45 peroxides R¹R²CHOOH, R¹R²CHOOR³, and R¹R²CHOOC(O)R³ (R¹, R² = H, Me, Et, Ph, H₂C=CH), the enthalpies of H atom abstraction from the C-H bond in the a-hydroperoxide fragment with fragmentation of the peroxides at the O-O bond were calculated. The kinetic parameters for 12 classes of radical abstraction reactions with fragmentation of molecules were calculated from experimental data within the framework of the model of intersecting parabolas. The activation energies and reaction rate constants of H atom abstraction from C-H bonds of a-peroxide fragments involving peroxyl and alkyl radicals were determined for 45 peroxides of different structure.     

Kinetics of hydrogen abstraction reactions of butene isomers by OH radical

The rate coefficients of H-abstraction reactions of butene isomers by the OH radical were determined by both canonical variational transition-state theory and transition-state theory, with potential energy surfaces calculated at the CCSD(T)/6-311++G(d,p)//BH&HLYP/6-311G(d,p) level and CCSD(T)/6-311++G(d,p)//BH&HLYP/cc-pVTZ level and quantum mechanical tunneling effect corrected by either the small-curvature tunneling method or the Eckart method. While 1-butene contains allylic, vinylic, and alkyl hydrogens that can be abstracted to form different butene radicals, results reveal that s-allylic H-abstraction channels have low and broad energy barriers, and they are the most dominant channels which can occur via direct and indirect H-abstraction channels. For the indirect H-abstraction s-allylic channel, the reaction can proceed via forming two van der Waals prereactive complexes with energies that are 2.7-2.8 kcal mol(-1) lower than that of the entrance channel at 0 K. Assuming that neither mixing nor crossover occurs between different reaction pathways, the overall rate coefficient was calculated by summing the rate coefficients of the s-allyic, methyl, and vinyl H-abstraction paths and found to agree well with the experimentally measured OH disappearance rate. Furthermore, the rate coefficients of p-allylic H abstraction of cis-2-butene, trans-2-butene, and isobutene by the OH radical were also determined at 300-1500 K, with results analyzed and compared with available experimental data.     

CuBr-catalyzed efficient alkynylation of sp3 C-H bonds adjacent to a nitrogen atom

A simple and effective catalytic method to construct propargylamine was developed by using copper bromide and tert-BuOOH via a combination of sp3 C-H bond and sp C-H bond activations followed by C-C bond formation.     

A theoretical study of hydrogen—atom abstraction by methyl radical

The activation energies for the abstraction of a hydrogen atom from each of several hydrocarbons has been calculated using the AM1 molecular orbital method. The calculated barrier for the abstraction from methane is 15.5 kcal/mole, in good agreement with experiment. Calculated barriers for other abstractions are reasonably good. They are much improved when the calculated intrinsic barrier is used together with the experimental heats of reaction in a modified formulation of Marcus theory.     

Catalytic enantioselective alkynylation of prochiral sp3 C-H bonds adjacent to a nitrogen atom

[reaction: see text] The construction of chiral carbon centers via the first catalytic asymmetric alkynylation of prochiral CH2 groups was developed by using a copper-catalyzed double activation of sp3 and sp C-H bonds. Optically active 1-alkynylated tetrahydroisoquinolines were obtained by this method.     

Direct arylation of unactivated aromatic C-H bonds catalyzed by a stable organic radical

A stable zwitterionic radical can catalyze direct arylation of unactivated aromatic C-H bonds via a chain homolytic aromatic substitution mechanism in the presence of potassium tert-butoxide.     

Theoretical study on the hydrogen abstraction reactions from hydrazine derivatives by H atom

The hydrogen abstraction reactions from hydrazine and its methyl derivatives by the H atom have been investigated theoretically by using CBS-QB3//DSD-BLYP-D3(BJ)/Def2-TZVP quantum chemical calculations and transition state theory calculations coupled with various tunneling correction methods. Both the products and transition state energies of the hydrogen abstraction from the amino group were stabilized by the methyl group substitution. The substitution effect on the ^αN site was two times larger than that on the ^βN site. On the other hand, the substitution effect was negligible on the hydrogen abstraction from the methyl group. The overall rate coefficients of N₂H₄ + H reaction calculated by canonical variational transition state theory with the small-curvature tunneling correction agreed well with previously reported values, but those of CH₃NHNH₂/(CH₃)₂NNH₂ + H were slightly lower than a previous experimental value. The product-specific rate coefficients have been proposed for the kinetics modeling of these fuels’ combustion.     

Investigations into the effectiveness of deuterium as a "protecting group" for C-H bonds in radical reactions involving hydrogen atom transfer

Competition experiments have been carried out to determine the extent to which deuterium can be used as a protecting group for carbon-hydrogen bonds in radical-based intramolecular hydrogen atom transfer processes.     

Estimations of OH radical rate constants from H-atom abstraction from C?H and O?H bonds over the temperature range 250-1000 K

Rate constants for overall H-atom abstraction by hydroxyl radicals from C? H and O? H bonds are estimated for alkanes, haloalkanes, aldehydes, ketones, ethers, alcohols, nitriles, and nitrates over thetemperature range 250–1000 K. These estimated rate constants utilize the modified Arrhenius expression K = A'T²e^?E'/T in combination with the recommendations given in the recent review and evaluation of OH radical kinetics of Atkinson [1]. This estimation procedure gives good agreement, generally to within better than a factor of 2, of the estimated rate constants with theserecommendations.     

Hydrogen atom abstraction from polypropylene and polystyrene by t-butoxy radical site of radical attack studied by spin trapping

In order to elucidate the site of radical attack on polypropylene and polystyrene, the abstractions of hydrogen atoms by t-butoxy radicals and phenyl radicals have been studied by using a spin trapping technique. The t-butoxy radical abstracted tertiary hydrogen atoms selectively from polypropylene, polystyrene and model compounds. On the other hand, the tertiary hydrogens in polypropylene and its model compounds were less reactive towards the phenyl radical than the secondary hydrogens within the same molecule and the secondary hydrogens in polystyrene were abstracted predominantly by the phenyl radical. The conformational effects on the reactivities of various hydrogens in polypropylene and model compounds were found to be similar.     

Reactivity of C-H bonds in cyclohexanone and 1-tert-butylperoxycyclohexanol toward the tert-butylperoxyl radical

The kinetics of oxygen uptake and the composition of the cyclohexanone oxidation products in the azobisisobutyronitrile-initiated oxidation of cyclohexanone in the presence of tert-butyl hydroperoxide have been investigated by the Howard-Ingold method. The partial rate constants of the reaction of the tert-butylperoxyl radical with the C-H bonds of cyclohexanol and 1-tert-butylperoxycyclohexanole at 333 K have been determined. The carbonyl group of cyclohexanone activates the C-H bonds in the 2- and 6-positions (α) and deactivates the C-H bonds in the 3- and 5-positions (β) compared to the C-H bonds in the 4-position (γ), whose reactivity is similar to that of the methylenic C-H bonds in cyclohexane. Evaluation of the joint effect of the hydroxyl and tert-butylperoxyl groups in 1-tert-butylperoxycyclohexanol suggests a considerable deactivation of the C-H bonds in the 2- and 6-positions (β) and, to a lesser extent, in the 3- and 5-positions (γ).     

Estimation of dissociation energies of C—H bonds in oxygen-containing compounds from kinetic data for radical abstraction reactions

The C—H bond dissociation energies were calculated on the basis of the parabolic model from the rate constants of free radical reactions for more than 160 oxygen-containing compounds. The enthalpies of formation of free radicals formed from these compounds were calculated. The method was modified taking into account the influence of functional groups on the partial rate constant and for the case when the reference reaction in the reaction series belongs to another class of structurally similar reactions.     

Reactions of the IO· radical resulting in hydrogen atom abstraction from halogen-containing molecules

A jet-stream kinetic technique and the resonance fluorescence method applied to detection of iodine atoms were used to measure the rate constants of the reactions of the IO^· radical with the halohydrocarbons CHFCl-CF₂Cl (k = (3.2 ± 0.9) × 10^?16 cm³ molecule s^?1) and CH₂ClF (k = (9.4 ± 1.3) × 10^?16 cm³ molecule s^?1), the hydrogen-containing haloethers CF₃-O-CH₃ (k = (6.4 ± 0.9) × 10^?16 cm³ molecule s^?1) and CF₃CH₂-O-CHF₂ (k = (1.2 ± 0.6) × 10^?15 cm³ molecule s^?1), and hydrogen iodide (k = (1.3 ± 0.9) × 10^?12 cm³ molecule s^?1) at 323 K.     

Attempts to prepare alkylidene zirconium complexes by α-hydrogen atom abstraction

We prepared several new neopentyl halide complexes of zirconium in order to test whether they could be induced to lose neopentane and give neopentylidene complexes by adding phosphorus or nitrogen donor ligands. ZrNp₂X₂ (X  Cl or Br) can be prepared in ether and isolated as a dietherate (an oil). It reacts with L (L  PMe₃, PMe₂Ph, NEt₃, $\text{1}\text{2}$ DMPE, $\text{1}\text{2}$ TMEDA) to give ZrNp₂X₂L₂. ZrNp₃Cl can be prepared by adding MgNp₂ to ZrNp₂Cl₂(ether)₂ and isolated by sublimation in 25% yield. On adding PMe₃ or TMEDA, it disproportionates to ZrNp₄ and ZrNp₂Cl₂L₂. ZrCp″NpCl₂ (Cp″ = η⁵-C₅Me₅), ZrCp″Np₂Cl, and ZrCp″Np₃ were prepared by adding MgNp₂ to ZrCp″Cl₃. Only the last is a solid, only the first forms an adduct, ZrCp″NpCl₂(PMe₃). None of the complexes decomposed to tractable products in the presence of L. Photolysis of ZrNp₂Cl₂(PMe₃)₂ yielded [Zr(PMe₃)₂Cl₃]₂ by an apparently complex reaction initiated by homolytic ZrNp bond fission.