Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan.
Chem Asian J. 2022 Jul 15;17(14):e202200305. doi: 10.1002/asia.202200305. Epub 2022 May 23.
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.
后功能化卟啉类催化剂为精细调整其电子结构提供了有力工具。我们已经成功地实现了钌和钴 5,15-二氮杂卟啉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第二次甲基化。二氮杂卟啉配合物的 N-甲基化有效地控制了其电子缺失、路易斯酸度和催化活性。
