Many hydrogen transfer processes exhibit nonclassical behavior due to inherent quantum mechanical properties of the hydrogen. Investigation of various enzymes under physiological conditions indicates that hydrogen transfer processes often show significant quantum mechanical behavior. Traditionally, this phenomenon was treated in terms of a tunneling correction to classical or semiclassical mode...

where H-H-C and H-D-C are weak bonds and make a negligible contribution, leads to a value of -2 kcal. Therefore, E5-E2=1 kcal compared with the experimental value of 1.0 kcal. The preexponential factor for this pair of isotopic reactions can be calculated from the difference in the entropies of activation. Using the same loose complex as above and applying the expression derived by Bigeleisens ...

In mass spectrometry of protonated N-phenylcinnamides, the carbonyl oxygen is the thermodynamically most favorable protonation site and the added proton is initially localized on it. Upon collisional activation, the proton transfers from the carbonyl oxygen to the dissociative protonation site at the amide nitrogen atom or the α-carbon atom, leading to the formation of important reactive interm...

Abstract We report the enantioselective total syntheses of preussomerins EG 1 , 2 and 3 . The key transformation is a stereospecific photochemical reaction involving 1,6‐hydrogen atom transfer to achieve retentive replacement C−H with C−O bond, enabling otherwise‐difficult control spiroacetal stereogenic center.

The photolytic formation of thiyl radicals allows for the selective detection of total homocysteine (tHcy) in plasma after reduction and filtering. The mechanism is based on the reduction of viologens by the α-amino carbon centred radical of Hcy generated by intramolecular hydrogen atom transfer (HAT) of its thiyl radical.

The reaction of a manganese(V)-oxo porphyrinoid complex with the Lewis acid B(C6F5)3 leads to reversible stabilization of the valence tautomer Mn(IV)(O)(π-radical cation). The latter complex, in combination with B(C6F5)3, reacts with ArO-H substrates via formal hydrogen-atom transfer and exhibits dramatically increased reaction rates over the Mn(V)(O) starting material.

A desoxomolybdenum(IV) complex containing bulky hydrophobic groups and NH···S hydrogen bonds, (Et4N)[Mo(IV)(OSi(t)BuPh2)(1,2-S2-3,6-{(4-(t)BuC6H4)3CCONH}2C6H2)2], was synthesized. This complex promotes the oxygen-atom-transfer (OAT) reaction of DMSO by efficient uptake of the substrate into the active center. The clean OAT reaction of Me3NO is also achieved.

The oxidation of phenols by HFeO4(-) proceeds via a hydrogen atom transfer (HAT) mechanism, as evidenced by a large deuterium isotope effect and a linear correlation between the log(rate constant) and bond dissociation free energy (BDFE) of phenols. The Marcus cross relation has been applied to predict the rate constant of HAT from hydroquinone to HFeO4(-).