Mechanistic Study of Arylsilane Oxidation through 19F NMR Spectroscopy [component]

The mechanism of the oxidation of arylsilanes to phenols has been investigated using 19 F NMR spectroscopy. The formation of silanols in these reactions results from a rapid background equilibrium between silanol and alkoxysilane; the relative rates of reaction of these species was evaluated by modeling of concentration profiles obtained through 19 F NMR spectroscopic reaction monitoring. Combining these results with a study of initial rates of phenol formation, and of substituent electronic
more » ... tuent electronic effects, a mechanistic picture involving rapid and reversible formation of a pentavalent peroxide ate complex, prior to rate-limiting aryl migration, has evolved.
doi:10.1021/jacs.7b00357.s001 fatcat:xfzdlsu5xrfajmprksnpfkpucu