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首页> 外文期刊>Spectrochimica acta, Part A. Molecular and biomolecular spectroscopy >Synthesis, spectroscopic characterization and ESR studies on electron transfer reactions of bis[N-(2,6-di-tert-butyl-1-hydroxyphenyl)salicylaldiminato]-copper(II) complexes with PbO2 and PPh3
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Synthesis, spectroscopic characterization and ESR studies on electron transfer reactions of bis[N-(2,6-di-tert-butyl-1-hydroxyphenyl)salicylaldiminato]-copper(II) complexes with PbO2 and PPh3

机译：PbO2和PPh3双[N-（2,6-二叔丁基-1-羟苯基）水杨基亚氨基]-铜（II）配合物的电子转移反应的合成，光谱表征和ESR研究

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New bis[N-(2,6-di-t-buty1-1-hydroxyphenyl)salicylideneminato]copper(II) complexes bearing HO and CH3O substituents on the salicyaldehyde moiety were prepared, and their spectroscopic properties, as well as redox reactivity towards PbO2 and PPh3, examined by ESR and UV spectroscopy. In the process of synthesis of HO complexes unlike CH,O the oxidative C-C coupling of coordinated salicylaldimine ligands does not takes place. The powder ESR spectra of CI-I,O substituted complexes unlike of HO analogues are typical of a triplet state Cu(II) dimers with a half-field forbidden (DeltaM = +/-2) transition and the allowed transitions (Deltam = +/-1) dimeric form of the complexes at 300 and 113 K. The one-electron oxidation of 3-CH3O and all of the OH complexes with PbO2 to give indophenoxyl type secondary radicals which are significantly different from those observed for analogues Cl, Br and NO2 substituted chelates. The presented complexes unlike their electron-withdrawing analogues are readily reduced by PPh3 via intramolecular electron transfer from ligand to copper(II) to give various radical intermediates as well as Cu(I) radical ligand compounds. The analysis of ESR spectra all of the complexes and radical intermediates are presented. (C) 2001 Elsevier Science B.V. All rights reserved. [References: 56]
机译：制备了新的在水杨醛部分带有HO和CH3O取代基的双[N-（2,6-二叔丁基1-1-羟基苯基）水杨基亚氨基]铜（II）配合物，其光谱性质以及对氧化还原反应性PbO2和PPh3，通过ESR和紫外光谱检查。在不同于CH，O的HO配合物的合成过程中，配位的水杨醛亚胺配体的氧化C-C偶联没有发生。 CI-1，O取代的配合物的粉末ESR谱不同于HO类似物，是具有三态禁态（DeltaM = +/- 2）跃迁和允许跃迁（Deltam = + / -1）在300和113 K时的复合物的二聚体形式。3-CH3O和所有OH配合物与PbO2的单电子氧化产生吲哚酚型二次自由基，这与类似物Cl，Br观察到的明显不同和NO2取代的螯合物。通过分子内电子从配体到铜（II）的分子内电子转移，PPh3可以很容易地还原所呈现的配合物与它们的吸电子类似物，从而得到各种自由基中间体以及Cu（I）自由基配体化合物。给出了所有配合物和自由基中间体的ESR谱图分析。 （C）2001 Elsevier Science B.V.保留所有权利。 [参考：56]

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