Stepwise N‐Methylation of Ruthenium and Cobalt 5,15‐Diazaporphyrins: Post‐Functionalization of Porphyrinoid Catalysts

Stepwise N‐Methylation of Ruthenium and Cobalt 5,15‐Diazaporphyrins: Post‐Functionalization of Porphyrinoid Catalysts
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钌和钴 5,15-二氮杂卟啉的逐步 N-甲基化:类卟啉催化剂的后功能化

DOI:
10.1002/asia.202200305
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发表时间:
2022
期刊:
Chemistry An Asian Journal
影响因子:
--
通讯作者:
Miyake Yoshihiro
Miyake Yoshihiro
中科院分区:
--
文献类型:
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作者:
Nishijo Mayu;Mori Shiho;Nishimura Tsubasa;Shinokubo Hiroshi;Miyake Yoshihiro

文献摘要

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类卟啉催化剂的后功能化为微调其电子结构提供了有力的工具。我们已经成功地在钌和钴5,15-二氮杂卟啉的外围氮原子的逐步甲基化。阴离子与金属中心的轴向配位通过电荷中和加速了二次甲基化反应,N-甲基化反应有效地控制了配合物的缺电子、刘易斯酸性和催化活性。
Post‐functionalization of porphyrinoid catalysts provides a powerful tool for fine‐tuning their electronic structure. We have succeeded in the stepwise methylation of the peripheral nitrogen atoms in ruthenium and cobalt 5,15‐diazaporphyrins. The axial coordination of an anion to the metal center accelerates the second methylation through charge neutralization.N‐Methylation of the diazaporphyrin complexes effectively controls their electron deficiency, Lewis acidity, and catalytic activity.