Unusual metalloporphycenes. First syntheses of carbonyl- and dioxo-containing osmium and ruthenium tetrapropylporphycene complexes
Unusual metalloporphycenes. First syntheses of carbonyl- and dioxo-containing osmium and ruthenium tetrapropylporphycene complexes
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不寻常的金属卟啉。
DOI：
10.1021/ic00038a070
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发表时间：
1992
影响因子：
4.6
通讯作者：
C. Chang
中科院分区：
文献类型：
--
作者：
Zaofei Li;Jie‐Sheng Huang;C. Che;C. Chang
卟啉是Vogel等人几年前首次合成的一种新型卟啉异构体，具有丰富的金属卟啉化学性质。[1]金属卟啉配合物与卟啉类似物的比较研究具有重要意义。2. Mn、Fe、Co、Ni、Cu、Zn、Pd、Pt等过渡金属被插入到卟啉配体中。[3]然而，相对较大的锇离子与卟啉的配位迄今尚未成功。这被认为是斑岩小空洞的证据。2.研究了十二羰基三锇[Os_3（CO）_（12）]与2，7，12，17-四丙基卟啉（H_2TPrPC）的反应，发现该反应很容易生成羰基锇（Ⅱ）卟啉配合物。与Ru 3（CO）2的类似反应也导致钌插入卟啉中。在这里，我们描述的第一个合成和表征的carbonylosmium和carbonylruthenium卟啉配合物和dioxooosmium（VI）卟啉配合物，其中金属具有前所未有的高氧化态的金属卟啉配合物。
Porphycene, a novel porphine isomer first synthesized by Vogel and co-workers several years ago, promises rich and colorful metalloporphycene chemistry. 1 It is of interest to study me-talloporphycene complexes in comparison with their porphyrin analogues. 2 A few transition metals, such as Mn, Fe, Co, Ni, Cu, Zn, Pd, and Pt, havebeen inserted into theporphycene ligand. 3 Coordination of the relatively large osmium ion with porphycene, however, has so far been unsuccessful. This was considered as evidence for the small cavity of porphycene. 2 In our study on the reaction of triosmiumdodecacarbonyl [Os3 (CO) 12] with 2, 7, 12, 17-tetrapropylporphycene (H2TPrPC), we found that this reaction readily afforded a carbonylosmium (II) porphycene complex. Similar reaction with Ru3 (CO), 2 also resultedin the insertion of ruthenium into porphycene. Here we describe the first synthesis and characterization of carbonylosmium and car-bonylruthenium porphycene complexes and a dioxoosmium (VI) porphycene complex in which the metal has an unprecedentedly high oxidation state in metalloporphycene complexes.