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首页> 外文期刊>Chemistry: A European journal >Mechanistic insights into the reversible formation of iodosylarene-iron porphyrin complexes in the reactions of oxoiron(IV) porphyrin pi-cation radicals and iodoarenes: Equilibrium, epoxidizing intermediate, and oxygen exchange
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Mechanistic insights into the reversible formation of iodosylarene-iron porphyrin complexes in the reactions of oxoiron(IV) porphyrin pi-cation radicals and iodoarenes: Equilibrium, epoxidizing intermediate, and oxygen exchange

机译：氧代铁（IV）卟啉π-阳离子自由基与碘芳烃反应中碘亚芳基-铁卟啉配合物可逆形成的机理研究：平衡，环氧化中间体和氧交换

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We have shown previously that iodosylbenzene-iron(iii) porphyrin intermediates (2) are generated in the reactions of oxoiron(iv) porphyrin 7ucation radicals (1) and iodobenzene (PhI), that 1 and 2 are at equilibrium in the presence of PhI, and that the epoxidation of olefins by 2 affords high yields of epoxide products. In the present work, we report detailed mechanistic studies on the nature of the equilibrium between 1 and 2 in the presence of iodoarenes (ArI), the determination of reactive species responsible for olefin epoxidation when two intermediates (i.e., 1 and 2) are present in a reaction solution, and the fast oxygen exchange between 1 and (H2O)-O-18 in the presence of ArI. In the first part, we have provided strong evidence that 1 and 2 are indeed at equilibrium and that the equilibrium is controlled by factors such as the electronic nature of iron porphyrins, the electron richness of ArI, and the concentration of ArI. Secondly, we have demonstrated that 1 is the sole active oxidant in olefin epoxidation when 1 and 2 are present concurrently in a reaction solution. Finally, we have shown that the presence of ArI in a reaction solution containing 1 and (H2O)-O-18 facilitates the oxygen exchange between the oxo group of 1 and (H2O)-O-18 and that the oxygen exchange is markedly influenced by factors such as ArI incubation. time, the amounts of ArI and (H2O)-O-18 used, and the electronic nature of ArI. The latter results are rationalized by the formation of an undetectable amount of 2 from the reaction of 1 and ArI through equilibrium that leads to a fast oxygen exchange between 2 and (H2O)-O-18.
机译：先前我们已经表明，碘代苯（铁）卟啉中间体（2）是在氧代铁（iv）卟啉7ucation自由基（1）与碘代苯（PhI）的反应中生成的，在PhI存在下1和2处于平衡状态并且，通过2的烯烃环氧化可提供高收率的环氧产物。在目前的工作中，我们报告了在碘代芳烃（ArI）存在下1和2之间平衡性质的详细机理研究，当存在两种中间体（即1和2）时，确定了负责烯烃环氧化的反应性物种在反应溶液中，在ArI存在下1与（H2O）-O-18之间进行快速的氧交换。在第一部分中，我们提供了有力的证据，证明1和2确实处于平衡状态，并且该平衡受诸如铁卟啉的电子性质，ArI的电子富集和ArI浓度等因素控制。其次，我们证明了当反应溶液中同时存在1和2时，1是烯烃环氧化的唯一活性氧化剂。最后，我们表明在包含1和（H2O）-O-18的反应溶液中ArI的存在促进了1和（H2O）-O-18的羰基之间的氧交换，并且氧交换受到显着影响受ArI孵化等因素影响。时间，ArI和（H2O）-O-18的用量以及ArI的电子性质。后者的结果是合理的，因为1与ArI的反应通过平衡形成了无法检测到的2，导致2与（H2O）-O-18之间快速进行氧交换。

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