[40]nonaphyrin(1.1.1.1.1.1.1.1.1) and its heterometallic complexes with palladium-carbon bonds
[40]nonaphyrin(1.1.1.1.1.1.1.1.1) and its heterometallic complexes with palladium-carbon bonds
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DOI：
10.1002/chem.200601304
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发表时间：
2007-01-01
影响因子：
4.3
通讯作者：
Osuka, Atsuhiro
中科院分区：
文献类型：
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作者：
Kamimura, Yiho;Shimizu, Soji;Osuka, Atsuhiro
meso-五氟苯基取代的[40]壬卟啉-（1.1.1.1.1.1.1.1）3已通过使用逐步环尺寸选择性合成制备，并已用NaBH还原为[42]壬卟啉（1.1.1.1.1.1.1.1.1）5。在结构上，3的特征在于8字形形状，由卟啉样四吡咯片段和六卟啉样六吡咯片段组成，而5已被发现采用扭曲的非平面蝴蝶状形状。在单金属配合物6和7中，Zn-II或Cu-II离子被卟啉样四吡咯片段结合，保持3的整体结构。与3类似，配合物6和7与相应的配合物9和10通过NaBH的双电子还原和DDQ的氧化而相互转化。6和7的不含金属的六卟啉样链段已被证明用作两个钯离子络合的合适平台，提供异三核金属络合物11（Zn-II-Pd-II-Pd-II）和13（Cu-II-Pd-II-Pd-II），其中Zn或Cu离子位于相同的卟啉样片段，一个Pd离子通过双C-H键活化以NNCC方式结合，而另一个Pd离子通过单C-H键活化以NNC方式结合。多金属配合物11、12和13尽管具有非平面构象，但表现出小的电化学HOMO-LUMO能隙（< 0.6 eV）。
meso-Pentafluorophenyl-substituted [40]nonaphyrin-(1.1.1.1.1.1.1.1.1) 3 has been prepared by using a stepwise ring-size-selective synthesis, and has been reduced with NaBH, to [42]nonaphyin(1.1.1.1.1.1.1.1.1.1) 5. Structurally, 3 is characterized by a figure-of-eight shape, consisting of a porphyrin-like tetrapyrrolic segment and a hexaphyrin-like hexapyrrolic segment, whereas 5 has been found to adopt a distorted nonplanar butterfly-like shape. In the mono-metal complexes 6 and 7, a Zn-II or Cu-II ion is bound by the porphyrin-like tetrapyrrolic segment, maintaining the overall structure of 3. Similarly to 3, complexes 6 and 7 are interconvertible with the corresponding complexes 9 and 10 through two-electron reduction with NaBH, and oxidation with DDQ. The metal-free hexaphyrin-like segments of 6 and 7 have been shown to serve as a suitable platform for the complexation of two palladium ions, providing hetero-trinuclear metal complexes 11 (Zn-II-Pd-II-Pd-II) and 13 (Cu-II-Pd-II-Pd-II) in high yields, in which the Zn or Cu ion resides at the same porphyrin-like segment, and one Pd ion is bound in an NNCC fashion through double C-H bond activation while the other is bound in an NNC fashion with single C-H bond activation. Multimetal complexes 11, 12, and 13 exhibit small electrochemical HOMO-LUMO gaps (< 0.6 eV), despite their nonplanar conformations.