The reactions of the asymmetrical 14- or 15-membered Ni(Ⅱ)-Xbenzotetraazaanulene with thiophenecarbonyl chlorides give the thiophenecarbonylated nickel(Ⅱ) complexes (X = 2CH3, CH3, H, Cl, 2Cl, NO2), and synthesized Ni(II)-Xbenzotetraazaannulene (C series) with dimethyl and dipheneyl. IR spectra of t...
The reactions of the asymmetrical 14- or 15-membered Ni(Ⅱ)-Xbenzotetraazaanulene with thiophenecarbonyl chlorides give the thiophenecarbonylated nickel(Ⅱ) complexes (X = 2CH3, CH3, H, Cl, 2Cl, NO2), and synthesized Ni(II)-Xbenzotetraazaannulene (C series) with dimethyl and dipheneyl. IR spectra of the thiophenecarbonylated compounds showed an intense band assigned to the stretching modes of C=O in the regions 1600 ~ 1640 cm-1. Hammett plots of the energies of π → π* and LMCT for the compounds were linear with positive and negative slopes. The methine sites proton signals of the new complexes are disappeared by thiophenecarbonylation. The methyl proton peaks are moved to upfield and the others porton peaks are shifted downfield owing to shielding or deshielding effect by thiophenecarbonylation. The results of the carbon-13 NMR spectra are compatible with those for the proton NMR spectra. Electrochemical properties of the complexes are carried out by the cyclic voltammetry in DMSO solutions. The cyclic voltammograms of the complexes were observed two one-electron irreversible oxidation processes by ligand based and one reversible reduction potential by metal based in the potential range from +1100 mV to -3000 mV. The Hammett plots showed positive slopes as substituents (2CH3, CH3, H, Cl, 2Cl, NO2) for the 1st and 2nd oxidation potentials by ligand based and reduction potentials by metal based. The 14- or 15-membered copper(II) and palladium(II) complexes were electropolymerized by cycling from +1.0 ~ -2.0 V in acetonitrile solutions giving thin films on the glassy carbon electrode surface similar to nickel(II) complexes. The surface modified electrodes by polymerizations showed strong electrocatalytic activities for dioxygen. in phosphate buffer solution (pH = 7.0, 25 ℃). For the reduction for dioxygen, the catalytic activity of 14-member copper(II) complex was higher than the others complexes in the range of 0 ~ -1.0 V. The surface modified electrodes by SAM appeared the complex with electrowithdrawing group better than the others for oxygen. Also, SAM electrode showed catalytic activity for homocystein in the range of +1.0 ~ 0.0 V. Hydrocarbon oxidations catalyzed by tetraaza[14]annulene metal(II) complexes have been investigated by substituents on styrenes. The total conversion(%) were decreased following OCH3 > CH3 > H > F > Cl for the substituted styrene. The 15-membered complexes were higher total conversion yields than those of 14-membered complexes. The metal ion effect on the catalytic activity of complex was increased in the order of Pd(II) < Ni(II) 2σ(I)], R1=0.0654 and wR2=0.1851, B5; crystal system, orthorhombic; space group, Pnma; α=β=γ=90°; R indices [I>2σ(I)], R1=0.0580 and wR2=0.1532, C2; crystal system, monoclinic; space group, P21/c; α=γ=90°; β=100.517°; R indices [I>2σ(I)], R1=0.0558 and wR2=0.1148, C3; crystal system, triclinic; space group, P1; α=104.502, β=99.804°, γ=111.822°; R indices [I>2σ(I)], R1=0.0548 and wR2=0.1386, C4; crystal system, triclinic; space group, P1; α=74.284, β=67.297°, γ=79.330°; R indices [I>2σ(I)], R1=0.0562 and wR2=0.1370) are determined by the single crystal X-ray diffraction method. The crystal structure data showed that the bond lengths between a nickel and two nitrogens of ethylenediamine group of the 14-membered complex was shorter than that between a nickel and tow nitrogen of phenylenediamine because of th difference of basicities for ethylenediamine (pKb1=4.11, pKb2=6.92) and phenylenediamine (pKb1=9.39, pKb2=12.19). While the bond lengths of a nickel and two nitrogen of phenylenediamine for the 15-membered complex was shorter than those of a metal and nitrogen of propylenediamine owing to ring strain of propylenediamine groups.
The reactions of the asymmetrical 14- or 15-membered Ni(Ⅱ)-Xbenzotetraazaanulene with thiophenecarbonyl chlorides give the thiophenecarbonylated nickel(Ⅱ) complexes (X = 2CH3, CH3, H, Cl, 2Cl, NO2), and synthesized Ni(II)-Xbenzotetraazaannulene (C series) with dimethyl and dipheneyl. IR spectra of the thiophenecarbonylated compounds showed an intense band assigned to the stretching modes of C=O in the regions 1600 ~ 1640 cm-1. Hammett plots of the energies of π → π* and LMCT for the compounds were linear with positive and negative slopes. The methine sites proton signals of the new complexes are disappeared by thiophenecarbonylation. The methyl proton peaks are moved to upfield and the others porton peaks are shifted downfield owing to shielding or deshielding effect by thiophenecarbonylation. The results of the carbon-13 NMR spectra are compatible with those for the proton NMR spectra. Electrochemical properties of the complexes are carried out by the cyclic voltammetry in DMSO solutions. The cyclic voltammograms of the complexes were observed two one-electron irreversible oxidation processes by ligand based and one reversible reduction potential by metal based in the potential range from +1100 mV to -3000 mV. The Hammett plots showed positive slopes as substituents (2CH3, CH3, H, Cl, 2Cl, NO2) for the 1st and 2nd oxidation potentials by ligand based and reduction potentials by metal based. The 14- or 15-membered copper(II) and palladium(II) complexes were electropolymerized by cycling from +1.0 ~ -2.0 V in acetonitrile solutions giving thin films on the glassy carbon electrode surface similar to nickel(II) complexes. The surface modified electrodes by polymerizations showed strong electrocatalytic activities for dioxygen. in phosphate buffer solution (pH = 7.0, 25 ℃). For the reduction for dioxygen, the catalytic activity of 14-member copper(II) complex was higher than the others complexes in the range of 0 ~ -1.0 V. The surface modified electrodes by SAM appeared the complex with electrowithdrawing group better than the others for oxygen. Also, SAM electrode showed catalytic activity for homocystein in the range of +1.0 ~ 0.0 V. Hydrocarbon oxidations catalyzed by tetraaza[14]annulene metal(II) complexes have been investigated by substituents on styrenes. The total conversion(%) were decreased following OCH3 > CH3 > H > F > Cl for the substituted styrene. The 15-membered complexes were higher total conversion yields than those of 14-membered complexes. The metal ion effect on the catalytic activity of complex was increased in the order of Pd(II) < Ni(II) 2σ(I)], R1=0.0654 and wR2=0.1851, B5; crystal system, orthorhombic; space group, Pnma; α=β=γ=90°; R indices [I>2σ(I)], R1=0.0580 and wR2=0.1532, C2; crystal system, monoclinic; space group, P21/c; α=γ=90°; β=100.517°; R indices [I>2σ(I)], R1=0.0558 and wR2=0.1148, C3; crystal system, triclinic; space group, P1; α=104.502, β=99.804°, γ=111.822°; R indices [I>2σ(I)], R1=0.0548 and wR2=0.1386, C4; crystal system, triclinic; space group, P1; α=74.284, β=67.297°, γ=79.330°; R indices [I>2σ(I)], R1=0.0562 and wR2=0.1370) are determined by the single crystal X-ray diffraction method. The crystal structure data showed that the bond lengths between a nickel and two nitrogens of ethylenediamine group of the 14-membered complex was shorter than that between a nickel and tow nitrogen of phenylenediamine because of th difference of basicities for ethylenediamine (pKb1=4.11, pKb2=6.92) and phenylenediamine (pKb1=9.39, pKb2=12.19). While the bond lengths of a nickel and two nitrogen of phenylenediamine for the 15-membered complex was shorter than those of a metal and nitrogen of propylenediamine owing to ring strain of propylenediamine groups.
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