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将硅烷基锂酰胺添加到1,2-二氰基苯中：通过核磁共振/ X射线衍射/密度泛函理论方法研究异吲哚啉-1,3-二亚胺衍生物

Addition of Lithium Silylamides to 1,2-Dicyanobenzene: Isoindoline-1,3-diimine Derivatives Investigated by NMR/XRD/DFT Approach.

作者信息

Majerová Stanislava, Chlupatý Tomáš, Samsonov Maksim A, Cvačka Josef, Procházková Eliška, Růžička Aleš

机构信息

Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, Pardubice 532 10, Czech Republic.

Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Flemingovo nám. 2, Prague 160 00, Czech Republic.

出版信息

Inorg Chem. 2025 Apr 21;64(15):7592-7606. doi: 10.1021/acs.inorgchem.5c00573. Epub 2025 Apr 8.

DOI:10.1021/acs.inorgchem.5c00573
PMID:40198575
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12015960/
Abstract

Phthalocyanines and their building blocks, isoindoline-1,3-diimines (diiminoisoindoles, DIIs), represent a structurally diverse class of compounds with the ability to make metal complexes and perform in various fields from medicine to photovoltaics and homogeneous catalysis. According to the present study, monosubstituted diiminoisoindoles, their higher homologues, and complexes can be effectively prepared by addition of silylated lithium amides to 1,2-dicyanobenzene followed by mild protonolysis or a condensation. An addition of DII to carbodiimides or reactions of lithiated DIIs with acyl chlorides give DII-guanidines and amido derivatives. The imino group of the amido derivatives is preferentially and quantitatively reduced by sodium borohydride. Dynamic behavior and structure of all studied classes of compounds were investigated from the stereochemical point of view─possible /-isomerization and dimerization (DIIs and amido derivatives), tautomerism (guanidines), and stability both in solution and in solid state. The resonance-assisted hydrogen bonds are present in all species except reduced amides, predetermining them to be exceptional ligands in coordination chemistry.

摘要

酞菁及其结构单元异吲哚啉-1,3-二亚胺（二亚氨基异吲哚，DIIs）是一类结构多样的化合物，能够形成金属配合物，并在从医学到光伏和均相催化等各个领域发挥作用。根据本研究，通过将硅烷基化的锂酰胺加入到1,2-二氰基苯中，随后进行温和的质子解或缩合反应，可以有效地制备单取代二亚氨基异吲哚、其高级同系物和配合物。将DII加入到碳二亚胺中或锂化的DII与酰氯反应可得到DII-胍和酰胺衍生物。酰胺衍生物的亚氨基优先被硼氢化钠定量还原。从立体化学的角度研究了所有研究的化合物类别的动态行为和结构——可能的/-异构化和二聚化（DIIs和酰胺衍生物）、互变异构（胍）以及在溶液和固态中的稳定性。除了还原酰胺外，所有物种中都存在共振辅助氢键，这使得它们在配位化学中成为特殊的配体。

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