Rudolf Richard, Neuman Nicolás I, Walter Robert R M, Ringenberg Mark R, Sarkar Biprajit
Lehrstuhl für Anorganische Koordinationschemie, Institut für Anorganische Chemie, University of Stuttgart, Pfaffenwaldring 55, 70569, Stuttgart, Germany.
Instituto de Desarrollo Tecnológico para la Industria Química, INTEC, UNL-CONICET Predio CONICET Santa Fe "Dr. Alberto Cassano", Colectora Ruta Nacional 168, Km 0, Paraje El Pozo, S3000ZAA) Santa Fe, Argentina.
Angew Chem Int Ed Engl. 2022 Jun 20;61(25):e202200653. doi: 10.1002/anie.202200653. Epub 2022 Apr 19.
We report the synthesis and the reactivity of 1,2,3-triazolin-5-imine type mesoionic imines (MIIs). The MIIs are accessible by a base-mediated cycloaddition between a substituted acetonitrile and an aromatic azide, methylation by established routes and subsequent deprotonation. C=O-stretching frequencies in MII-CO and -Rh(CO) Cl complexes were used to determine the overall donor strength. The MIIs are stronger donors than the N-heterocyclic imines (NHIs). MIIs are excellent ligands for main group elements and transition metals in which they display substituent-induced fluorine-specific interactions and undergo C-H activation. DFT calculations gave insights into the frontier orbitals of the MIIs. The calculations predict a relatively small HOMO-LUMO gap compared to other related ligands. MIIs are potentially able to act as both π-donor and π-acceptor ligands. This report highlights the potential of MIIs to display exciting properties with a huge potential for future development.
我们报道了1,2,3-三唑啉-5-亚胺型中氮茚亚胺（MIIs）的合成及其反应活性。通过取代乙腈与芳基叠氮化物之间的碱介导环加成反应、既定路线的甲基化以及随后的去质子化反应可制得MIIs。利用MII-CO和-Rh(CO)Cl配合物中的C=O伸缩频率来确定整体给体强度。MIIs是比N-杂环亚胺（NHIs）更强的给体。MIIs是主族元素和过渡金属的优良配体，在其中它们表现出取代基诱导的氟特异性相互作用并发生C-H活化。密度泛函理论（DFT）计算深入了解了MIIs的前沿轨道。计算预测与其他相关配体相比，其最高占据分子轨道（HOMO）-最低未占据分子轨道（LUMO）能隙相对较小。MIIs有潜力同时作为π给体和π受体配体。本报告突出了MIIs展现令人兴奋的性质以及未来巨大发展潜力的可能性。
