Stable meso-meso-Linked 2NH-Corrole Radical Dimers as a Key Intermediate to Corrole Tape.,Angewandte Chemie International Edition

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Stable meso-meso-Linked 2NH-Corrole Radical Dimers as a Key Intermediate to Corrole Tape.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-03-13 , DOI: 10.1002/anie.202002976
Shota Ooi ₁ , B Adinarayana ₁ , Daiki Shimizu ₁ , Takayuki Tanaka ₁ , Atsuhiro Osuka ₁

Affiliation

While oxidation of 5,5′,15,15′‐tetramesityl‐10‐10′‐linked 3NH‐corrole dimer with DDQ gave the corresponding triply linked 2NH‐corrole tape, the use of an equimolar amount of p‐chloranil as a milder oxidant resulted in the formation of a 10‐10′‐linked neutral 2NH‐corrole radical dimer as a stable product. The stability of this peculiar product is ascribed largely to strong antiferromagnetic interaction of the two spins. Further oxidation of this diradical produced corrole tape, suggesting its involvement as a reaction intermediate to the corrole tape. Oxidation of 10‐10′‐linked bis‐pyridine‐coordinated Co^III corrole dimer with DDQ produced a cobalt corrole radical dimer and a doubly linked corrole dimer both as stable compounds bearing pyridine and cyanide axial ligands. This type of oxidative transformation involving neutral diradical intermediates is a unique reaction mechanism specific for corrole dimers.

中文翻译：

稳定的介观介导的2NH-Corrole自由基二聚体是Corrole胶带的关键中间体。

用DDQ氧化5,5'，15,15'-四甲基1-10-10'-连接的3NH-corrole二聚体可得到相应的三链连接的2NH-corrole胶带，但使用等摩尔量的对氯苯胺温和些氧化剂导致形成10-10'-连接的中性2NH-Corrole自由基二聚体，成为稳定的产物。该独特产物的稳定性很大程度上归因于两个自旋的强反铁磁相互作用。该双基产生的腐蚀带进一步氧化，表明它作为腐蚀带的反应中间体参与其中。10-10'-连接的双吡啶配位的Co ^III的氧化带有DDQ的Corrole二聚体可生成钴Corrole自由基二聚体和双连接的Corrole二聚体，两者都是带有吡啶和氰化物轴向配体的稳定化合物。这种涉及中性双自由基中间体的氧化转化是特定于Corrole二聚体的独特反应机理。

更新日期：2020-03-13

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