Share this post on:

His contrasts with his earlier definition that “the term `H-atom transfer’ refers to what is transferred between reactants in the net sense and not to the mechanism of the event.”18 However, the restrictive definition is problematic in many cases. For instance, often the two particles comeChem Rev. Author manuscript; available in PMC 2011 December 8.Warren et al.Pagefrom the same bond but are not in the same bond in the product. One example is hydrogen atom abstraction from C bonds by compound I in cytochrome P450 enzymes, where the proton transfers from carbon to the oxygen of the ferryl (Fe=O) group but the electron is transferred to the porphyrin radical cation.23 Under the restrictive “same bond” definition the reaction would be HAT in the forward direction but not in the reverse, which is a problem. Furthermore, it is often difficult to determine whether the electron and proton are “in the same bond.” In removing H?from phenols, for example, the e- and H+ are in the same bond when the O bond lies in a plane perpendicular to the aromatic ring, but they are not in the same bond when the O lies in the plane of the aromatic ring. In phenol itself the hydrogen is in the plane, but how would reactions of the common 2,6-di-tert-butylsubstituted phenols be classified? Similarly, classification of H?removal from the vanadyl hydroxide complex [(bpy)2VIV(O)(OH)]+ would depend on the OV torsion angle.24 In the minimum energy structure, the O bond is calculated to have a torsion angle of 45?vs. the orbital with the transferring electron, which precludes conclusions about `being in the same bond.’ To avoid these confusions, we prefer the definition implied in Scheme 2, that `hydrogen atom transfer’ indicates concerted transfer of H+ and e- from a single donor to a single acceptor. 2.3 Separated CPET There are also concerted transfers of 1e- + 1H+ in which the proton and electron transfer to (or from) different reagents. In Scheme 3, for instance, XH is oxidized with the electron being transferred to oxidant Y while the proton is transferred to base B. One of the more widely discussed biological examples is the photosynthetic oxidation of tyrosine-Z where an electron is transferred to a photoexcited chlorophyll (P680+) as the phenolic proton is thought to transfer to a nearby H-bonded histidine residue.25 Babcock’s discussion of the thermochemistry of this process is a landmark in the development of biological PCET chemistry.26 Such `separated CPET’ reactions are clearly distinct from HAT reactions. These have also been termed “multisite EPT.”1a However, there are an increasing number of reactions that fall in a grey area between HAT and separated CPET, such as the reaction in eq 3.27 This reaction involves concerted transfer of e- and H+ (H? from the O bond of 2,4,6-tri-t-butylphenol to a ruthenium(III) complex, so this reaction could formally be called HAT. From another perspective, however, the proton is transferred to a carboxylate oxygen that is 11 ?removed from the ruthenium center that accepts the electron, and there is essentially no communication between these sites,27 so in some ways this is better described as a separated CPET process.NIH-PA Author Luteolin 7-O-��-D-glucoside chemical information Manuscript NIH-PA Author Manuscript NIH-PA Author Manuscript(3)3. L868275 biological activity Thermochemical BackgroundThe thermochemistry of a 1H+/1e- PCET reagent XH in a given solvent is described by five parameters, as shown in Scheme 4. These are: the acidity/basicity of the oxidized andChem Rev. Author man.His contrasts with his earlier definition that “the term `H-atom transfer’ refers to what is transferred between reactants in the net sense and not to the mechanism of the event.”18 However, the restrictive definition is problematic in many cases. For instance, often the two particles comeChem Rev. Author manuscript; available in PMC 2011 December 8.Warren et al.Pagefrom the same bond but are not in the same bond in the product. One example is hydrogen atom abstraction from C bonds by compound I in cytochrome P450 enzymes, where the proton transfers from carbon to the oxygen of the ferryl (Fe=O) group but the electron is transferred to the porphyrin radical cation.23 Under the restrictive “same bond” definition the reaction would be HAT in the forward direction but not in the reverse, which is a problem. Furthermore, it is often difficult to determine whether the electron and proton are “in the same bond.” In removing H?from phenols, for example, the e- and H+ are in the same bond when the O bond lies in a plane perpendicular to the aromatic ring, but they are not in the same bond when the O lies in the plane of the aromatic ring. In phenol itself the hydrogen is in the plane, but how would reactions of the common 2,6-di-tert-butylsubstituted phenols be classified? Similarly, classification of H?removal from the vanadyl hydroxide complex [(bpy)2VIV(O)(OH)]+ would depend on the OV torsion angle.24 In the minimum energy structure, the O bond is calculated to have a torsion angle of 45?vs. the orbital with the transferring electron, which precludes conclusions about `being in the same bond.’ To avoid these confusions, we prefer the definition implied in Scheme 2, that `hydrogen atom transfer’ indicates concerted transfer of H+ and e- from a single donor to a single acceptor. 2.3 Separated CPET There are also concerted transfers of 1e- + 1H+ in which the proton and electron transfer to (or from) different reagents. In Scheme 3, for instance, XH is oxidized with the electron being transferred to oxidant Y while the proton is transferred to base B. One of the more widely discussed biological examples is the photosynthetic oxidation of tyrosine-Z where an electron is transferred to a photoexcited chlorophyll (P680+) as the phenolic proton is thought to transfer to a nearby H-bonded histidine residue.25 Babcock’s discussion of the thermochemistry of this process is a landmark in the development of biological PCET chemistry.26 Such `separated CPET’ reactions are clearly distinct from HAT reactions. These have also been termed “multisite EPT.”1a However, there are an increasing number of reactions that fall in a grey area between HAT and separated CPET, such as the reaction in eq 3.27 This reaction involves concerted transfer of e- and H+ (H? from the O bond of 2,4,6-tri-t-butylphenol to a ruthenium(III) complex, so this reaction could formally be called HAT. From another perspective, however, the proton is transferred to a carboxylate oxygen that is 11 ?removed from the ruthenium center that accepts the electron, and there is essentially no communication between these sites,27 so in some ways this is better described as a separated CPET process.NIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author Manuscript(3)3. Thermochemical BackgroundThe thermochemistry of a 1H+/1e- PCET reagent XH in a given solvent is described by five parameters, as shown in Scheme 4. These are: the acidity/basicity of the oxidized andChem Rev. Author man.

Share this post on:

Author: calcimimeticagent