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Steric Effect on the Nucleophilic Reactivity of Nickel(III) Peroxo Complexes

Title
Steric Effect on the Nucleophilic Reactivity of Nickel(III) Peroxo Complexes
Authors
Kim, J[Kim, Jalee]Shin, B[Shin, Bongki]Kim, H[Kim, Hyunjeong]Lee, J[Lee, Junhyung]Kang, J[Kang, Joongoo]Yanagisawa, S[Yanagisawa, Sachiko]Ogura, T[Ogura, Takashi]Masuda, H[Masuda, Hideki]Ozawa, T[Ozawa, Tomohiro]Cho, J[Cho, Jaeheung]
DGIST Authors
Kim, J[Kim, Jalee]; Shin, B[Shin, Bongki]; Kim, H[Kim, Hyunjeong]; Lee, J[Lee, Junhyung]; Kang, J[Kang, Joongoo]; Cho, J[Cho, Jaeheung]
Issue Date
2015-07-06
Citation
Inorganic Chemistry, 54(13), 6176-6183
Type
Article
Article Type
Article
Keywords
Chemical StructureChemistryHydrogen PeroxideMacrocyclic CompoundMacrocyclic CompoundsModels, MolecularNickelOrganometallic CompoundOrganometallic CompoundsOxidation-ReductionOxidation-Reduction ReactionQuantum Theory
ISSN
0020-1669
Abstract
A set of nickel(III) peroxo complexes bearing tetraazamacrocyclic ligands, [NiIII(TBDAP)(O2)]+ (TBDAP = N,N′-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane) and [NiIII(CHDAP)(O2)]+ (CHDAP = N,N′-dicyclohexyl-2,11-diaza[3.3](2,6)pyridinophane), were prepared by reacting [NiII(TBDAP)(NO3)(H2O)]+ and [NiII(CHDAP)(NO3)]+, respectively, with H2O2 in the presence of triethylamine. The mononuclear nickel(III) peroxo complexes were fully characterized by various physicochemical methods, such as UV-vis, electrospray ionization mass spectrometry, resonance Raman, electron paramagnetic resonance, and X-ray analysis. The spectroscopic and structural characterization clearly shows that the NiO2 cores are almost identical where the peroxo ligand is bound in a side-on fashion. However, the different steric properties of the supporting ligands were confirmed by X-ray crystallography, where the CHDAP ligand gives enough space around the Ni core compared to the TBDAP ligand. The nickel(III) peroxo complexes showed reactivity in the oxidation of aldehydes. In the aldehyde deformylation reaction, the nucleophilic reactivity of the nickel(III) peroxo complexes was highly dependent on the steric properties of the macrocyclic ligands, with a reactivity order of [NiIII(TBDAP)(O2)]+ < [NiIII(CHDAP)(O2)]+. This result provides fundamental insight into the mechanism of the structure (steric)-reactivity relationship of metal peroxo intermediates. (Figure Presented). © 2015 American Chemical Society.
URI
http://hdl.handle.net/20.500.11750/2340
DOI
10.1021/acs.inorgchem.5b00294
Publisher
American Chemical Society
Files:
There are no files associated with this item.
Collection:
Emerging Materials ScienceComputational Materials Theory Group1. Journal Articles


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