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Title: Characterization and Reactivity of a Terminal Nickel(III)-Oxygen Adduct

Abstract

Here, 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 Ni II-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 Ni III–oxygen adduct. Moreover, 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.

Authors:
 [1];  [2];  [3];  [4];  [4];  [1]
  1. Univ. of Dublin (Ireland)
  2. Case Western Reserve Univ., Cleveland, OH (United States)
  3. Univ. of Girona (Spain)
  4. Univ. College Dublin (Ireland)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1228948
Report Number(s):
BNL-111023-2015-JA
Journal ID: ISSN 0947-6539
Grant/Contract Number:  
AC02–98CH10886; SC00112704; P30-EB-009998; UNGI08–4E-003; 2014SGR1202; CTQ2011–25086/BQU; CM1305; SFI/12/RC/2278
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 21; Journal Issue: 9; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Pirovano, Paolo, Farquhar, Erik R., Swart, Marcel, Fitzpatrick, Anthony J., Morgan, Grace G., and McDonald, Aidan R. Characterization and Reactivity of a Terminal Nickel(III)-Oxygen Adduct. United States: N. p., 2015. Web. doi:10.1002/chem.201406485.
Pirovano, Paolo, Farquhar, Erik R., Swart, Marcel, Fitzpatrick, Anthony J., Morgan, Grace G., & McDonald, Aidan R. Characterization and Reactivity of a Terminal Nickel(III)-Oxygen Adduct. United States. doi:10.1002/chem.201406485.
Pirovano, Paolo, Farquhar, Erik R., Swart, Marcel, Fitzpatrick, Anthony J., Morgan, Grace G., and McDonald, Aidan R. Thu . "Characterization and Reactivity of a Terminal Nickel(III)-Oxygen Adduct". United States. doi:10.1002/chem.201406485. https://www.osti.gov/servlets/purl/1228948.
@article{osti_1228948,
title = {Characterization and Reactivity of a Terminal Nickel(III)-Oxygen Adduct},
author = {Pirovano, Paolo and Farquhar, Erik R. and Swart, Marcel and Fitzpatrick, Anthony J. and Morgan, Grace G. and McDonald, Aidan R.},
abstractNote = {Here, 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. Moreover, 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.},
doi = {10.1002/chem.201406485},
journal = {Chemistry - A European Journal},
number = 9,
volume = 21,
place = {United States},
year = {2015},
month = {1}
}

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