- ニッケル(III)アセテート錯体だそうです。
- Tollmanが最近使っている配位子系ですね。
- Paolo Pirovano1,
- Dr. Erik R. Farquhar2,
- Prof. Marcel Swart3,
- Anthony J. Fitzpatrick4,
- Dr. Grace G. Morgan4 and
- Dr. Aidan R. McDonald1,*
Keywords:
- high-valent metals;
- metal–oxo species;
- nickel;
- oxidation catalysis;
- reactive intermediates
- high-valent metals;
- metal–oxo species;
- nickel;
- oxidation catalysis;
- reactive intermediates
Abstract
High-valent terminal metal–oxygen adducts are hypothesized to be the potent oxidizing reactants in late transition metal oxidation catalysis. In particular, examples of high-valent terminal nickel–oxygen adducts are scarce, meaning there is a dearth in the understanding of such oxidants. A monoanionic NiII-bicarbonate complex has been found to react in a 1:1 ratio with the one-electron oxidant tris(4-bromophenyl)ammoniumyl hexachloroantimonate, yielding a thermally unstable intermediate in high yield (ca. 95 %). Electronic absorption, electronic paramagnetic resonance, and X-ray absorption spectroscopies and density functional theory calculations confirm its description as a low-spin (S=), square planar NiIII–oxygen adduct. This rare example of a high-valent terminal nickel–oxygen complex performs oxidations of organic substrates, including 2,6-di-tert-butylphenol and triphenylphosphine, which are indicative of hydrogen atom abstraction and oxygen atom transfer reactivity, respectively.
High-valent terminal metal–oxygen adducts are hypothesized to be the potent oxidizing reactants in late transition metal oxidation catalysis. In particular, examples of high-valent terminal nickel–oxygen adducts are scarce, meaning there is a dearth in the understanding of such oxidants. A monoanionic NiII-bicarbonate complex has been found to react in a 1:1 ratio with the one-electron oxidant tris(4-bromophenyl)ammoniumyl hexachloroantimonate, yielding a thermally unstable intermediate in high yield (ca. 95 %). Electronic absorption, electronic paramagnetic resonance, and X-ray absorption spectroscopies and density functional theory calculations confirm its description as a low-spin (S=), square planar NiIII–oxygen adduct. This rare example of a high-valent terminal nickel–oxygen complex performs oxidations of organic substrates, including 2,6-di-tert-butylphenol and triphenylphosphine, which are indicative of hydrogen atom abstraction and oxygen atom transfer reactivity, respectively.
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Chem.–Eur. J. Ni
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Chem.–Eur. J.
Ni
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