6533b821fe1ef96bd127c28d

RESEARCH PRODUCT

Synyhesis, structure, spectroscopy and redox chemistry of square-planar nickel(II) complexes with tetradentate o-phenylenedioxamidates and related ligands

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description

[EN] A series of four-coordinate square-planar nickel(II) complexes of o-phenylenebis(N¿-methyloxamidate) (L1) and related o-phenylene(N¿-methyloxamidate)oxamate (L2) and o-phenylenebis(oxamate) (L3) tetradentate ligands have been synthesized and characterized structurally, spectroscopically and electrochemically. The parent nickel(II)¿L1 complex presents an intense MLCT band in the UV region (¿max = 357 nm) and a distinctive 1 s ¿ 4p CT satellite in the Ni K-edge XANES spectrum (E = 8339.2 eV). These features together with the short Ni¿N(amidate) bond lengths (1.85¿1.93 Å) as revealed by the analysis of the Ni K-edge EXAFS spectrum and confirmed by single-crystal X-ray diffraction are typical of square-planar low spin (S = 0) NiII ions. The dianionic nickel(II) complexes, [NiIILi]2¿ (i = 1¿3), experience two redox processes in acetonitrile at 25 °C. The first redox process, at moderately low potentials (E1 = 0.12¿0.52 V vs. SCE), is a reversible one-electron metal-centered oxidation to the corresponding monoanionic nickel(III) complexes, [NiIIILi]¿. The second redox process, at relatively high potentials (E2 = 0.86¿1.04 V vs. SCE), is a quasireversible to irreversible one-electron oxidation largely centered on the o-benzenediamidate fragment of the non-innocent ligand, yielding the corresponding neutral nickel(III) complexes with a o-benzosemiquinonediimine ¿-cation radical ligand, [NiIII(Li)¿+]. The singly and doubly oxidized species of the parent nickel(II)¿L1 complex have been prepared by chemical oxidation and characterized spectroscopically in acetonitrile at ¿40 °C. The stable singly oxidized nickel(III)¿L1 species presents an intense LMCT band in the NIR region (¿max = 910 nm) and a rhombic X-band EPR spectrum (g1 = 2.193, g2 = 2.080 and g3 = 2.006) characteristic of square-planar low spin (S = 1/2) NiIII ions. The unstable double oxidized nickel(III)¿L1 ¿-cation radical species exhibits a rather intense visible band (¿max = 645 nm) that is tentatively assigned as a MLCT transition from the NiIII-benzosemiquinone type ground state to the NiIV excited state.