DUGiDocsCharacterization and reactivity of a terminal nickel(III)-oxygen adduct
Full Text
Characterization-and-Reactivity.pdf
Request a copy
When filling the form you are requesting a copy of the article, that is deposited in the institutional repository (DUGiDocs), at the autor or main autor of the article. It will be the same author who decides to give a copy of the document to the person who requests it, if it considers it appropriate. In any case, the UdG Library doesn’t take part in this process because it is not authorized to provide restricted articles.
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 = 1/2 ), 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
Tots els drets reservats