Radical [1,3] Rearrangements of Breslow Intermediates

Stabilization of Free Radical Intermediates

Free radicals intermediates are formed on the surface of metal oxide semiconductors, namely Ti02 and Fe203, following the light-induced charge separation upon band-gap illu-mination. These radicals appear to adhere strongly to the ~.urfaces of the small colloidal particles (diameters between 5 and 20 nm) employed in this study. A second electron-transfer step yielding the observed end-products ...

A Mechanochemical Switch to Control Radical Intermediates

B₁₂-dependent enzymes employ radical species with exceptional prowess to catalyze some of the most chemically challenging, thermodynamically unfavorable reactions. However, dealing with highly reactive intermediates is an extremely demanding task, requiring sophisticated control strategies to prevent unwanted side reactions. Using hybrid quantum mechanical/molecular mechanical simulations, we f...

Nitrene Radical Intermediates in Catalytic Synthesis

Nitrene radical complexes are reactive intermediates with discrete spin density at the nitrogen-atom of the nitrene moiety. These species have become important intermediates for organic synthesis, being invoked in a broad range of C-H functionalization and aziridination reactions. Nitrene radical complexes have intriguing electronic structures, and are best described as one-electron reduced Fis...

Spectroscopic and Kinetic Investigations of Conjugated Bi Radical Intermediates

Several reactive biradical intermediates of photochemical reactions were monitored directly in solution by the technique of kinetic and time—resolved spectrographic laser flash photolysis, and identified with the aid of low—temperature epr and optical spectroscopy, semiempirical calculations, as well as conventional steady—state analyses of product distributions. The focus of this report is on ...

Radical intermediates in monooxygenase reactions of rieske dioxygenases.