Copper(II) complexes of inverted porphyrin and its methylated derivatives
Copper(II) complexes of inverted porphyrin and its methylated derivatives
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DOI：
10.1021/ic000051x
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发表时间：
2000-11-27
影响因子：
4.6
通讯作者：
Schmidt, I
中科院分区：
文献类型：
--
作者：
Chmielewski, PJ;Latos-Grazynski, L;Schmidt, I
反向卟啉2-氮杂-5,10,15,20-四苯基-21-碳卟啉(CTPPH2)及其甲基化衍生物2-氮杂-2-甲基-5,10,15,20-四苯基-21-碳卟啉(2-NCH3CTPPH)和2-氮杂-2-甲基-5,10,15,20-四苯基-21-甲基-21-碳卟啉 (2-NCH3-21-CH3CTPPH) 可稳定稀有有机铜(II) 配合物 (CTPP)Cu-II (1)、(2-NCH3CTPP)Cu-II (2)、(CTPPH)(CuX)-X-II (3-X)、 (2-NCH3CTPPH)(CuX)-X-II (4-X) (X = Cl-, TFA) 和 (2-NCH3-21-CH3CTPP)(CuCl)-Cl-II (5)，1、2、4 和 5 记录的 EPR 谱揭示了铜 (II) 电子结构的典型诊断特征。超超精细耦合模式表明第一配位层中存在三个氮供体。将 HX 酸添加到 1 和 2 中，得到物质 3-X 和 4-X。反应机理包括内部 C(21) 碳的质子化伴随着阴离子的轴向配位，(2-NCH3CTPP)Cu-II (2) 与碘甲烷的甲基化导致形成 (2-NCH3-21-CH3CTPP)(CuCl)-Cl-II (5)，这意味着 2 中存在 σ -碳负离子 - 铜 (II) 键。 H-2 NMR 研究为吡咯氘化衍生物(CTPP-d(7))Cu-II、(2-NCH3-21-CH3CTPP-d(7))Cu-II-Cl和甲基氘化(2-NCH3-21-CD3CTPP)(CuCl)-Cl-II独立证实了铜(II)电子结构，对SOMO具有相当大的d(x2-y2)金属轨道贡献。采用循环和微分脉冲伏安法研究了铜(II)反转卟啉的氧化还原性质。半波电位表明 1 (390 mV) 和 2 (343 mV) 的金属中心氧化。二甲基化同系物 5 揭示了由 Cu-II/Cu-I 转化引起的 -224 mV 还原过程。
The inverted porphyrins 2-aza-5,10,15,20-tetraphenyl-21-carbaporphyrin (CTPPH2) and its methylated derivatives 2-aza-2-methyl-5,10,15,20-tetraphenyl-21-carbaporphyrin (2-NCH3CTPPH) and 2-aza-2-methvl-5,10,15,20-tetraphenyl-21-methyl-21-carbaporphyrin (2-NCH3-21-CH3CTPPH) stabilize the rare organocopper(II) complexes (CTPP)Cu-II (1), (2-NCH3CTPP)Cu-II (2), (CTPPH)(CuX)-X-II (3-X), (2-NCH3CTPPH)(CuX)-X-II (4-X) (X = Cl-, TFA), and (2-NCH3-21-CH3CTPP)(CuCl)-Cl-II (5), The EPR spectra recorded for 1, 2, 4, and 5 revealed typical features diagnostic of the copper(II) electronic structure. The superhyperfine coupling pattern indicates a presence of three nitrogen donors in the first coordination sphere. An addition of HX acid to 1 and 2 to yield the species 3-X and 4-X. The reaction mechanism includes protonation of the inner C(21) carbon accompanied by an axial coordination of anion, Methylation of (2-NCH3CTPP)Cu-II (2) with methyl iodide resulted in formation of (2-NCH3-21-CH3CTPP)(CuCl)-Cl-II (5) which implies an existence of a sigma -carbanion-copper(II) bond in 2. The H-2 NMR investigations carried out for the pyrrole deuterated derivatives (CTPP-d(7))Cu-II, (2-NCH3-21-CH3CTPP-d(7))Cu-II-Cl, and the methyl deuterated (2-NCH3-21-CD3CTPP)(CuCl)-Cl-II one confirmed independently the copper(II) electronic structure with the considerable d(x2-y2) metal orbital contribution to the SOMO. The redox properties of copper(II) inverted porphyrins were studied by the cyclic and differential pulse voltammetry. The halfwave potentials indicate a metal-centered oxidation of 1 (390 mV) and 2 (343 mV). The dimethylated homologue 5 reveals the reduction process at -224 mV attributed to the Cu-II/Cu-I transformation.