TY - JOUR
T1 - A dianionic dinickel(II) complex and its oxidised phenoxyl radical states
AU - Benisvy, Laurent
AU - Wanke, Riccardo
AU - Guedes Da Silva, M. Fátima C.
AU - Pombeiro, Armando J.L.
PY - 2011/6
Y1 - 2011/6
N2 - The new dianionic dinickel(II) complex [NBu4] 2[Ni2(L)2] {L3- = trianionic form of 3,5-di-tert-butyl-2-hydroxy-N-(2-hydroxyethyl)benzamide} has been synthesised and characterised by 1H, 13C NMR and IR spectroscopy, mass spectrometry, elemental analysis and X-ray crystallography. The X-ray structure of [NBu4]2[Ni2(L)2] ·EtOH·CH3CN reveals a quasiplanar dinickel(II) dianionic complex, each of the NiII ions possessing a NO3 planar coordination sphere that results from the ligation of L3- in a NO2 fashion through the N-amidate, O-phenolate and O-bridging alcoholate donor atoms. The cyclic voltammogram of [Ni2(L) 2]2- reveals two one-electron reversible oxidation processes at relatively low potentials. The EPR and UV/Vis spectroscopic characterisations of the electrochemically generated one-electron- and two-electron-oxidised products are consistent with two ligand-based oxidation processes leading to the formation of relatively stable mono- and diphenoxyl radical complexes, [Ni2(L·)(L)]- and [Ni2(L·)2], respectively.
AB - The new dianionic dinickel(II) complex [NBu4] 2[Ni2(L)2] {L3- = trianionic form of 3,5-di-tert-butyl-2-hydroxy-N-(2-hydroxyethyl)benzamide} has been synthesised and characterised by 1H, 13C NMR and IR spectroscopy, mass spectrometry, elemental analysis and X-ray crystallography. The X-ray structure of [NBu4]2[Ni2(L)2] ·EtOH·CH3CN reveals a quasiplanar dinickel(II) dianionic complex, each of the NiII ions possessing a NO3 planar coordination sphere that results from the ligation of L3- in a NO2 fashion through the N-amidate, O-phenolate and O-bridging alcoholate donor atoms. The cyclic voltammogram of [Ni2(L) 2]2- reveals two one-electron reversible oxidation processes at relatively low potentials. The EPR and UV/Vis spectroscopic characterisations of the electrochemically generated one-electron- and two-electron-oxidised products are consistent with two ligand-based oxidation processes leading to the formation of relatively stable mono- and diphenoxyl radical complexes, [Ni2(L·)(L)]- and [Ni2(L·)2], respectively.
KW - Anions
KW - Nickel
KW - Polyanionic ligands
KW - Radicals
KW - Redox chemistry
UR - http://www.scopus.com/inward/record.url?scp=79958258705&partnerID=8YFLogxK
U2 - 10.1002/ejic.201100232
DO - 10.1002/ejic.201100232
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AN - SCOPUS:79958258705
SN - 1434-1948
SP - 2791
EP - 2796
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 18
ER -