Catalytic electronic activation

Stabilized nucleophiles have been added to allylic alcohols using catalytic electronic activation , in which a reaction has been designed where an alcohol is temporarily oxidized to a carbonyl compound.313... 

All the hydrogen transfer reactions shown highlight the potential for application of copper-supported catalysts as hydrogen reservoir systems. This leads to the possibility of applying the concept of catalytic electronic activation introduced by Williams and realizing sequences of domino transformations that accomplish otherwise impossible reactions [84, 85]. 

Pershad, H. R., Duff, J. L., Heering, H. A., Duin, E. C., Albracht, S. P. and Armstrong, F. A. (1999) Catalytic electron transport in Chromatium vinosum [NiFe]-hydrogenase Application of voltammetry in detecting redox-active centers and establishing that hydrogen oxidation is very fast even at potentials close to the reversible H+/H2 value. Biochemistry, 38, 8992-9. 

The peroxyoxalate system is the only intermolecular chemiluminescent reaction presumably involving the (71EEL sequence (Scheme 44), which shows high singlet excitation yields (4>s), as confirmed independently by several authors Moreover, Stevani and coworkers reported a correlation between the singlet quantum yields, extrapolated to infinite activator concentrations (4> ), and the free energy involved in back electron-transfer (AG bet), as well as between the catalytic electron-transfer/deactivation rate constants ratio, ln( cAx( i3), and E j2° (see Section V). A linear correlation of ln( cAx( i3) and E /2° was obtained for the peroxyoxalate reaction with TCPO and H2O2 catalyzed by imidazole and for the imidazole-catalyzed reaction of 57, both in the presence of five activators commonly used in CIEEL studies (anthracene, DPA, PPO, perylene and rubrene). A further confirmation of the validity of the CIEEL mechanism in the excitation step of... 

Selective carbon dioxide reduction to CO has been accomplished in a non-aqueous medium that includes tricarbonyl (2,2 -bipyridinium) rhenium , /ac-Re(bpy) (CO)3X (X=Cl, Br) as light-active component and homogeneous catalyst for C02 reduction [183-185]. In dimethylformamide solutions that include TEOA as sacrificial electron donor, photosensitized reduction of C02 to CO proceeds with a quantum efficiency of

Mechanistic investigations have revealed that reductive ET quenching of the rhenium complex (Eq. (54)) yields the catalytic intermediate active in deoxygenation of C02. It has been suggested that carbon... 

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