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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >CHEMISTRY OF A AZOIMIDAZOLES - SYNTHESIS, SPECTRAL CHARACTERIZATION AND REDOX PROPERTIES OF BIS(N(1)-ALKYL-2-(ARYLAZO)IMIDAZOLE) COPPER(I) AND SILVER(I) COMPLEXES
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CHEMISTRY OF A AZOIMIDAZOLES - SYNTHESIS, SPECTRAL CHARACTERIZATION AND REDOX PROPERTIES OF BIS(N(1)-ALKYL-2-(ARYLAZO)IMIDAZOLE) COPPER(I) AND SILVER(I) COMPLEXES

机译:偶氮咪唑的化学-双(N(1)-烷基-2-(芳基咪唑)咪唑)铜(I)和银(I)络合物的合成,光谱表征和氧化还原性质

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N(1)-Alkyl-2(arylazo)imidazoles p-C6H4N=NC3H2N N(1)R', RaaiR', R'=Me (2), Et (3); R=H(a), Me(b), OMe(c), Cl(d), NO2(e) yield catonic bis-chelated complexes with both copper(I) (4,5) and silver(I) (6,7). These were isolated as perchlorate salts and the composition is supported by elemental analyses. The complexes are 1:1 electrolytes in methanol. The N=N stretch in copper(I) complexes shows a large shift to lower frequency (ca 1335 cm(-1)) from the free ligand value (ca 1400 cm(-1)) due to d(Cu) --> pi(*) (RaaiR') back bonding. This effect is much less pronounced in silver(I) complexes indicating a negligible d pi-pi(*) (RaaiR') interaction. The complexes show highly resolved symmetrical H-1 NMR spectra. The copper(I) complexes exhibit intense MLCT transitions in the visible region. In methanol the Cu(RaaiR')(2)(2+)/Cu(RaaiR')(2)(+) couple has E-1/2 ca 0.45 V vs SCE at 298 K. The high positive potential may be due to the distortion in the geometry of Cu(RaaiR)(2)(+). (C) 1997 Elsevier Science Ltd. [References: 45]
机译:N(1)-烷基-2(芳基偶氮)咪唑p-C6H4N = NC3H2N N(1)R',RaaiR',R'= Me(2),Et(3); R = H(a),Me(b),OMe(c),Cl(d),NO2(e)生成具有铜(I)(4,5)和银(I)的阳离子双螯合络合物(6 ,7)。将其分离为高氯酸盐,并通过元素分析支持该组合物。配合物是甲醇中1:1的电解质。铜(I)络合物中的N = N展宽表明由于d(Cu)而从游离配体值(ca 1400 cm(-1))向较低频率(ca 1335 cm(-1))发生了很大变化-> pi(*)(RaaiR')背面键合。在银(I)络合物中这种作用不那么明显,表明d pi-pi(*)(RaaiR')相互作用可忽略不计。配合物显示高度分辨的对称H-1 NMR光谱。铜(I)配合物在可见光区域表现出强烈的MLCT过渡。在甲醇中,Cu(RaaiR')(2)(2 +)/ Cu(RaaiR')(2)(+)对在298 K下的SCE值为E-1 / 2 ca 0.45 V vs. SCE。高正电位可能是由于导致Cu(RaaiR)(2)(+)的几何变形。 (C)1997 Elsevier Science Ltd. [参考:45]

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