The reaction of CuX (X=Cl, Br, I) with a mixture of PPh3 and 1-alkyl-2-(naphthyl-α/β-azo)imidazol... more The reaction of CuX (X=Cl, Br, I) with a mixture of PPh3 and 1-alkyl-2-(naphthyl-α/β-azo)imidazole has synthesized mixed ligand complexes of the composition, [Cu(α/β-NaiR)(PPh3)X]. The spectroscopic characterization (IR, UV–Vis, 1H NMR) supports this formulation. The single crystal X-ray diffraction study of [Cu((α-NaiMe)(PPh3)I] (7a) (α-NaiMe=1-methyl-2-(naphthyl-α-azo)imidazole) shows a distorted tetrahedral geometry about Cu(I). Cyclic voltammograms of the complexes show a high potential Cu(II)/Cu(I) couple and azo reductions. The [Cu(α/β-NaiR)(PPh3)I] complexes show an additional oxidative response at 0.4V that is assigned to I/I− A sharp anodic peak at ∼−0.2V is assigned to the oxidation of metallic Cu, deposited on electrode surface upon scanning to the negative side of the SCE. DFT and TD-DFT computations of [Cu((α-NaiMe)(PPh3)I] (7a), [Cu((α-NaiMe)(PPh3)I]+ (7a+) and [Cu((α-NaiMe)(PPh3)I]− (7a−) were carried out to examine the electronic configuration and to explain the spectral and redox properties of the complexes.
ABSTRACT Reaction of CuX (X = Cl, Br, I), PPh3 and 2-(arylazo)pyridine, R-H4C6NNC5H4N (aap, 1 whe... more ABSTRACT Reaction of CuX (X = Cl, Br, I), PPh3 and 2-(arylazo)pyridine, R-H4C6NNC5H4N (aap, 1 where R = H (pap), p-Me (p-tap), m-Me (m-tap)) has synthesized [Cu((aap)(PPh3)X]. The structure has been established by spectroscopic (UV-Vis, 1H NMR) data and by single crystal X-ray diffraction of [Cu((pap)(PPh3)Br]. Addition of H2O2 to [Cu((aap)(PPh3)Cl] has afforded blue Cu(II) complexes, [Cu(aapO)(PPh3)Cl]. These complexes have been characterized by elemental analyses, IR, UV-Vis spectral and magnetic data. Upon addition of H2S saturated dil. H2SO4 solution to [Cu(aapO)(PPh3)Cl] free aapOH is separated and has been characterized by spectral data. Cyclic voltammogram of [Cu((aap)(PPh3)X] shows Cu(II)/Cu(I) response at 1.00-1.15 V and azo reduction at negative to SCE. DFT calculation of optimized structure of a representative complex has been used to determine the composition and energy of molecular levels and data have been used to explain the electronic spectral and redox properties.
The reaction of CuX (X=Cl, Br, I) with a mixture of PPh3 and 1-alkyl-2-(naphthyl-α/β-azo)imidazol... more The reaction of CuX (X=Cl, Br, I) with a mixture of PPh3 and 1-alkyl-2-(naphthyl-α/β-azo)imidazole has synthesized mixed ligand complexes of the composition, [Cu(α/β-NaiR)(PPh3)X]. The spectroscopic characterization (IR, UV–Vis, 1H NMR) supports this formulation. The single crystal X-ray diffraction study of [Cu((α-NaiMe)(PPh3)I] (7a) (α-NaiMe=1-methyl-2-(naphthyl-α-azo)imidazole) shows a distorted tetrahedral geometry about Cu(I). Cyclic voltammograms of the complexes show a high potential Cu(II)/Cu(I) couple and azo reductions. The [Cu(α/β-NaiR)(PPh3)I] complexes show an additional oxidative response at 0.4V that is assigned to I/I− A sharp anodic peak at ∼−0.2V is assigned to the oxidation of metallic Cu, deposited on electrode surface upon scanning to the negative side of the SCE. DFT and TD-DFT computations of [Cu((α-NaiMe)(PPh3)I] (7a), [Cu((α-NaiMe)(PPh3)I]+ (7a+) and [Cu((α-NaiMe)(PPh3)I]− (7a−) were carried out to examine the electronic configuration and to explain the spectral and redox properties of the complexes.
ABSTRACT Reaction of CuX (X = Cl, Br, I), PPh3 and 2-(arylazo)pyridine, R-H4C6NNC5H4N (aap, 1 whe... more ABSTRACT Reaction of CuX (X = Cl, Br, I), PPh3 and 2-(arylazo)pyridine, R-H4C6NNC5H4N (aap, 1 where R = H (pap), p-Me (p-tap), m-Me (m-tap)) has synthesized [Cu((aap)(PPh3)X]. The structure has been established by spectroscopic (UV-Vis, 1H NMR) data and by single crystal X-ray diffraction of [Cu((pap)(PPh3)Br]. Addition of H2O2 to [Cu((aap)(PPh3)Cl] has afforded blue Cu(II) complexes, [Cu(aapO)(PPh3)Cl]. These complexes have been characterized by elemental analyses, IR, UV-Vis spectral and magnetic data. Upon addition of H2S saturated dil. H2SO4 solution to [Cu(aapO)(PPh3)Cl] free aapOH is separated and has been characterized by spectral data. Cyclic voltammogram of [Cu((aap)(PPh3)X] shows Cu(II)/Cu(I) response at 1.00-1.15 V and azo reduction at negative to SCE. DFT calculation of optimized structure of a representative complex has been used to determine the composition and energy of molecular levels and data have been used to explain the electronic spectral and redox properties.
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