双子座 Sc/P 刘易斯对与吡啶四氮唑及其他的反应

IF 4.3 3区 材料科学 Q1 ENGINEERING, ELECTRICAL & ELECTRONIC ACS Applied Electronic Materials Pub Date : 2024-11-06 DOI:10.1039/d4dt02838d
Yiwen Guan, Xian Xu, Xin Xu
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引用次数: 0

摘要

受挫路易斯对(FLP)化学经历了显著的发展,其中以稀土金属为基础的路易斯对近年来表现出独特的反应活性。在本文中,分子内 Sc/P Lewis 对(即 (ArO)2ScN(tBu)PPh2 (1, Ar = 2,6-tBu2-C6H3))与吡啶四氮唑处理后,形成了具有 N2 消去作用的 FLP 芘加合物,为过渡金属催化吡啶四氮唑的脱氮环化机制提供了更多的见解。复合物 1 与 1,3,5-三嗪和苯并[c]噌啉的反应分别通过 C=N 键和 N=N 键的 Sc/P 1,2 加成生成了 FLP 型产物。此外,还研究了 1 与苯乙炔、重氮和叠氮化合物的处理,结果形成了多种具有典型 FLP 行为的金属环配合物。
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Reactions of a Geminal Sc/P Lewis Pair with Pyridotetrazole and Beyond
Frustrated Lewis pair (FLP) chemistry has undergone remarkable growth, among which rare-earth metal-based Lewis pairs have exhibited unique reactivity in recent years. Herein, treatment of the intramolecular Sc/P Lewis pair, i.e., (ArO)2ScN(tBu)PPh2 (1, Ar = 2,6-tBu2-C6H3), with pyridotetrazole resulted in the formation of an FLP nitrene adduct with N2 elimination, offering additional insights into the mechanism of transition-metal-catalyzed denitrogenative annulation of pyridotetrazole. Reactions of complex 1 with 1,3,5-triazine and benzo[c]cinnoline generated FLP-type products via Sc/P 1,2-addition to the C=N bond and the N=N bond, respectively. Furthermore, treatments of 1 with phenylacetylene, diazo, and azide compounds were also investigated, leading to the formation of a variety of metallacyclic complexes displaying typical FLP behaviors.
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来源期刊
CiteScore
7.20
自引率
4.30%
发文量
567
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