Hydrogen-transfer processes

The racemization mechanism of sec-alcohols has been widely studied [16,17]. Metal complexes of the main groups of the periodic table react through a direct transfer of hydrogen (concerted process), such as aluminum complexes in Meerwein-Ponn-dorf-Verley-Oppenauer reaction. However, racemization catalyzed by transition metal complexes occurs via hydrogen transfer processes through metal hydrides or metal dihydrides intermediates (Figure 4.5) [18]. 

With some transition-metal complexes, the ligand is not only an ancillary ligand. Similar to the transition-metal, it takes directly part in the hydrogen transfer process. Such ligand-metal bifunctional hydrogenation catalysis is dramatically changing the face of reduction chemistry (Scheme 9) (for reviews of ligand-metal bifunctional catalysis, see [32, 37 0]). 

Other enantioselective reactions performed by microwave heating include asymmetric Heck reactions (Scheme 6.53 a) [109] and ruthenium-catalyzed asymmetric hydrogen-transfer processes (Scheme 6.53 b) [110]. 

Isotopes in Organic Chemistry, 2, Isotopes in Hydrogen Transfer Process", E. Buncel and C. C. Lee, Eds., Elsevier Scientific Publishing Co., Amsterdam and New York, (1976). 

The valid criteria for estabhshing tunneling in hydrogen-transfer processes that have... 

Recent studies, however, indicate that the oxidation of methanol takes place by an electron transfer followed by a hydrogen-transfer process [Eqs. (42)-(44)]. 

Recently, the influence of the preparation method of various MgO samples on their catalytic activity in the MPV reaction of cyclohexanone with 2-propanol has been reported 202). The oxides were prepared by various synthetic procedures including calcination of commercially available magnesium hydroxide and magnesium carbonate calcination of magnesium hydroxides obtained from magnesium nitrate and magnesium sulfate sol-gel synthesis and precipitation by decomposition of urea. It was concluded that the efficiency of the catalytic hydrogen transfer process was directly related to the number of basic sites in the solid. Thus, the MgO (MgO-2 sample in Table IV) prepared by hydration and subsequent calcination of a MgO sample that had been obtained from commercially available Mg(OH)2 was the most basic and the most active for the MPV process, and the MgO samples with similar populations of basic sites exhibited similar activities (Table IV). 

D. Shemesh and R. B. Gerber. Classical trajectory simulations of photoionization dynamics of tryptophan intramolecular energy flow, hydrogen-transfer processes and conformational transitions, J. Phys. Chem. A, 110 8401-8408 (2006). 

Molecular hydrogen is not the only source of hydrogen since other molecules such as alcohols can also be used as a hydrogen source. In that case, one refers to hydrogen-transfer reactions. In the hydrogen-transfer processes, a donor species DH2 transfers two hydrogen molecules to an acceptor species A (Scheme 3). 

These reactions are most common for polar double bond as reactants (carbonyls and imines) than for non-polar substrates (alkene and alkyne). Hence, hydrogen-transfer processes are a very interesting option in order to perform polar double bond hydrogenation since they allow mild conditions, high selectivity,... 

Nevertheless, the mechanism of the Shvo s catalyst has been one of the most controversial regarding the nature of the hydrogen-transfer process (84). The analysis of this reaction mechanism served as an example of comparison of both the inner- and outer-sphere reaction pathways for hydrogenation of polar, C=0 (85-87) and C=N (88—95) and unpolar bonds (95). In the next subsections are presented the mechanistic studies we carried out for the hydrogenation of ketones, imines, alkenes, and alkynes (29,87,95). 

In both light and high energy irradiation induced reactions, phenyl-thiol, 2-mercaptomesitylene, and their sulfides inhibit nonchain processes,201202 e.g., the light-induced conversion of benzophenone in 2-propanol to benzopinacol and acetone.99 217 The reaction converts compounds into radicals by removal or addition of hydrogen atoms. The sulfur compounds in rapid hydrogen transfer processes convert the free radicals to stable molecules and may do so repeatedly.46 46... 

This observation can be used to derive a possible reaction mechanism for the hydrogen transfer process. We assume that the first step is the dehydrogenation of the alcoholic group, followed by isomerization of the unsaturated ketone to the conjugated one ... 

An unusual isomerization of perhydro[2.2]paracyclophane 29, an out-in hydrogen transfer process, was observed in triflic acid123 [Eq. (5.53)]. Reaction in CF3SO3D resulted in the incorporation of up to five deuteriums without specific locations. The authors suggested the backside attack of the inside hydrogen (Hj) to the bridgehead... 

Intra- and intermolecular hydrogen transfer processes are important in a wide variety of chemical processes, ranging from free radical reactions (which make up the foundation of radiation chemistry) and tautomeriza-tion in the ground and excited states (a fundamental photochemical process) to bulk and surface diffusion (critical for heterogeneous catalytic processes). The exchange reaction H2 + H has always been the preeminent model for testing basic concepts of chemical dynamics theory because it is amenable to carrying out exact three-dimensional fully quantum mechanical calculations. This reaction is now studied in low-temperature solids as well. 

In contrast, because of similar electronegativities, the transition state for hydrogen transfer from benzene thiol to a perfluoro-n-alkyl radical should have little polar character. In confirming the important role of polar effects in these hydrogen transfer processes, a good Hammett correlation was observed for the reduction of n- c7f15i by a series of arene thiols [141,143]. 

As a consequence, there may be synergistic interactions between the components of the different macerals in oxidative hydrogen transfer processes. 

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