Mesoionic Imines (MIIs): Strong Donors and Versatile Ligands for Transition Metals and Main Group Substrates
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 freque...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2022 |
| País: | Argentina |
| Institución: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/215943 |
| Acceso en línea: | http://hdl.handle.net/11336/215943 |
| Access Level: | acceso abierto |
| Palabra clave: | C−H ACTIVATION ELECTRONIC AMBIVALENCE FLUORINE SPECIFIC INTERACTIONS MESOIONIC IMINES STRONG DONORS https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Sumario: | 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−CO2 and −Rh(CO)2Cl 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. |
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