Item
Ministerio de Ciencia e Innovación (Espanya)
Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca |
|
Pirovano, Paolo
Farquhar, Erik R. Swart, Marcel Fitzpatrick, Anthony J. Morgan, Grace G. McDonald, Aidan R. |
|
2015 | |
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 |
|
application/pdf | |
http://hdl.handle.net/10256/11456 | |
eng | |
Wiley-VCH Verlag | |
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 |
|
Tots els drets reservats | |
Oxidació
Oxidation Catà lisi Catalysis NÃquel -- Oxidació Nickel -- Oxidation Metalls de transició -- Oxidació Transition metals -- Oxidation |
|
Characterization and reactivity of a terminal nickel(III)-oxygen adduct | |
info:eu-repo/semantics/article | |
DUGiDocs |