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Characterization and reactivity of a terminal nickel(III)-oxygen adduct

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

This publication has emanated from research supported in part by the European Union (FP7-333948, AMcD), a research grant from Science Foundation Ireland (SFI/12/RC/2278, AMcD), and COST Action CM1305 (ECOSTBio). M.S. acknowledges MINECO (CTQ2011-25086/BQU), DIUE of the Generalitat de Catalunya (2014SGR1202), MICINN (Ministry of Science and Innovation, Spain), the FEDER fund (UNGI08-4E-003) and CESCA. Operation of NSLS X3B is supported by NIH grant P30-EB-009998. The NSLS is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-98CH10886

Wiley-VCH Verlag

Manager: Ministerio de Ciencia e Innovación (Espanya)
Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca
Author: Pirovano, Paolo
Farquhar, Erik R.
Swart, Marcel
Fitzpatrick, Anthony J.
Morgan, Grace G.
McDonald, Aidan R.
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 = 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
This publication has emanated from research supported in part by the European Union (FP7-333948, AMcD), a research grant from Science Foundation Ireland (SFI/12/RC/2278, AMcD), and COST Action CM1305 (ECOSTBio). M.S. acknowledges MINECO (CTQ2011-25086/BQU), DIUE of the Generalitat de Catalunya (2014SGR1202), MICINN (Ministry of Science and Innovation, Spain), the FEDER fund (UNGI08-4E-003) and CESCA. Operation of NSLS X3B is supported by NIH grant P30-EB-009998. The NSLS is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-98CH10886
Format: application/pdf
Document access: http://hdl.handle.net/10256/11456
Language: eng
Publisher: Wiley-VCH Verlag
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.201406485
info:eu-repo/semantics/altIdentifier/issn/0947-6539
info:eu-repo/semantics/altIdentifier/eissn/1521-3765
info:eu-repo/grantAgreement/MICINN//CTQ2011-25086/ES/MODELIZACION MULTIESCALAR EN (BIO)QUIMICA/
AGAUR/2014-2017/2014SGR1202
Rights: Tots els drets reservats
Subject: Oxidació
Oxidation
Catàlisi
Catalysis
Níquel -- Oxidació
Nickel -- Oxidation
Metalls de transició -- Oxidació
Transition metals -- Oxidation
Title: Characterization and reactivity of a terminal nickel(III)-oxygen adduct
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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