A mononuclear nonheme cobalt(iii)-hydroperoxide complex with an amphoteric reactivity in electrophilic and nucleophilic oxidative reactions.
نویسندگان
چکیده
A mononuclear nonheme cobalt(iii)-hydroperoxide complex bearing a tetramethylated cyclam ligand, [(12-TMC)Co(III)(OOH)](2+), was synthesized and characterized spectroscopically and computationally; the cobalt(iii)-hydroperoxide complex exhibited an amphoteric reactivity in electrophilic and nucleophilic oxidative reactions.
منابع مشابه
Spectroscopic Characterization and Reactivity Studies of a Mononuclear Nonheme Mn(III)–Hydroperoxo Complex
We report the first example of a mononuclear nonheme manganese(III)-hydroperoxo complex derived from protonation of an isolated manganese(III)-peroxo complex bearing an N-tetramethylated cyclam (TMC) ligand, [Mn(III)(TMC)(OOH)](2+). The Mn(III)-hydroperoxo intermediate is characterized with various spectroscopic methods as well as with density functional theory (DFT) calculations, showing the b...
متن کاملNucleophilic reactivity of a copper(II)-superoxide complex.
Metal-bound superoxide intermediates are often implicated as electrophilic oxidants in dioxygen-activating metalloenzymes. In the nonheme iron α-ketoglutarate dependent oxygenases and pterin-dependent hydroxylases, however, Fe(III)-superoxide intermediates are postulated to react by nucleophilic attack on electrophilic carbon atoms. By reacting a Cu(II)-superoxide complex (1) with acyl chloride...
متن کاملSynthesis, structural, and spectroscopic characterization and reactivities of mononuclear cobalt(III)-peroxo complexes.
Metal-dioxygen adducts are key intermediates detected in the catalytic cycles of dioxygen activation by metalloenzymes and biomimetic compounds. In this study, mononuclear cobalt(III)-peroxo complexes bearing tetraazamacrocyclic ligands, [Co(12-TMC)(O(2))](+) and [Co(13-TMC)(O(2))](+), were synthesized by reacting [Co(12-TMC)(CH(3)CN)](2+) and [Co(13-TMC)(CH(3)CN)](2+), respectively, with H(2)O...
متن کاملTuning reactivity and mechanism in oxidation reactions by mononuclear nonheme iron(IV)-oxo complexes.
Mononuclear nonheme iron enzymes generate high-valent iron(IV)-oxo intermediates that effect metabolically important oxidative transformations in the catalytic cycle of dioxygen activation. In 2003, researchers first spectroscopically characterized a mononuclear nonheme iron(IV)-oxo intermediate in the reaction of taurine: α-ketogultarate dioxygenase (TauD). This nonheme iron enzyme with an iro...
متن کاملHighly reactive nonheme iron(III) iodosylarene complexes in alkane hydroxylation and sulfoxidation reactions.
High-spin iron(III) iodosylarene complexes bearing an N-methylated cyclam ligand are synthesized and characterized using various spectroscopic methods. The nonheme high-spin iron(III) iodosylarene intermediates are highly reactive oxidants capable of activating strong C-H bonds of alkanes; the reactivity of the iron(III) iodosylarene intermediates is much greater than that of the corresponding ...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Dalton transactions
دوره 45 37 شماره
صفحات -
تاریخ انتشار 2016