Kinetics and Mechanism of Oxidation of Anilines by Hydrogen Peroxide As Catalyzed by Methylrhenium Trioxide

Structure/function correlations among coupled binuclear copper proteins through spectroscopic and reactivity studies of NspF

“…Calculations specifically compared the electrophilic attack of a dioxygen derived oxygen atom on either the arene 2-position carbon (for the monophenolase reaction) or the 2-position amine (hydroxyanilinase reaction). The calculated reaction trajectories predict transition states consistent with electrophilic attacks, as observed in model studies of these reactions (10,21). Insight into the geometric requirements for hydroxyanilinase versus monophenolase activity comes from superposition of the transition states from these two reaction pathways (Fig.…”

“…While Cu 2 O 2 model complexes have also been shown to be competent for one-electron oxidations of substrate in a net-hydrogen atom abstraction mechanism (25)(26)(27), the oxidation of amino-phenols to iminoquinones is a two-electron process (28) and the oxidation of aryl-amines to the corresponding nitroso product by peroxide model complexes proceeds via an electrophilic mechanism (21). This suggests that the oxygenation of oaminophenols by NspF proceeds via an electrophilic mechanism.…”

Nitroxide synthesis using the methyltrioxorhenium/hydrogen peroxide system

“…This proposal is supported by the observations of Espenson and coworkers. In their studies of the oxidation of a series of anilines by the MTO-H 2 O 2 system, Zhu and Espenson [11] used a Hammett plot to show that the reaction was electrophilic in character. Also Al-Ajilouni and Espenson [20] have shown that epoxidation of alkenes by the metal system is an electrophilic process.…”

“…The MTO-H 2 O 2 system has been used to oxidize a variety of organic substrates including alkenes [5], phosphines, arsines, and stibines [6], arenes [7], sulfur compounds [8], benzaldehyde [9], alkynes [10], anilines [11], and alcohols [12]. In our work to date, comparing the MTO-H 2 O 2 system with dimethyldioxirane, we have shown that the metal system is capable of carrying out a C-H insertion reaction [13] in the same manner as the dioxirane.…”

Probing Ionic Diffusion Dynamics through the Modulation of Polymer Shell Using Surface-Enhanced Raman Spectroscopy

“…We postulate that they could be dimer or trimers, of very small amounts, owning to the absence of characteristics IR peaks between ~690 and 750 cm -1 of monosubstitured aromatic rings [29,30]. Additionally, the presence of the hydrogen peroxide as oxidant could also help to support the formation of nitrosobenzene [31]. Therefore, it is believed that a range of compounds derived from aniline could be present in the soft-shell.…”