Open AccessMechanistic Study of Arylsilane Oxidation through 19F NMR Spectroscopy
Author(s) -
Elizabeth J. Rayment,
Aroonroj Mekareeya,
Nick Summerhill,
Edward A. Anderson
Publication year - 2017
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.7b00357
Subject(s) - chemistry , silanol , fluorine 19 nmr , peroxide , nuclear magnetic resonance spectroscopy , substituent , phenol , phenols , reaction mechanism , spectroscopy , aryl , limiting , proton nmr , photochemistry , computational chemistry , organic chemistry , catalysis , mechanical engineering , engineering , physics , alkyl , quantum mechanics
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 effects, a mechanistic picture involving rapid and reversible formation of a pentavalent peroxide ate complex, prior to rate-limiting aryl migration, has evolved.