Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions
We present herein anionic borate-based bi-mesoionic carbene compounds of the 1,2,3-triazol-4-ylidene type that undergo C−N isomerization reactions. The isomerized compounds are excellent ligands for CoII centers. Strong agostic interactions with the “C−H”-groups of the cyclohexyl substituents result...
| Autores: | , , , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2020 |
| País: | Argentina |
| Institución: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/127930 |
| Acceso en línea: | http://hdl.handle.net/11336/127930 |
| Access Level: | acceso abierto |
| Palabra clave: | COBALT LIGAND REARRANGEMENT MESOIONIC CARBENE REACTIVITY SPIN STATE https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Sumario: | We present herein anionic borate-based bi-mesoionic carbene compounds of the 1,2,3-triazol-4-ylidene type that undergo C−N isomerization reactions. The isomerized compounds are excellent ligands for CoII centers. Strong agostic interactions with the “C−H”-groups of the cyclohexyl substituents result in an unusual low-spin square planar CoII complex, which is unreactive towards external substrates. Such agostic interactions are absent in the complex with phenyl substituents on the borate backbone. This complex displays a high-spin tetrahedral CoII center, which is reactive towards external substrates including dioxygen. To the best of our knowledge, this is also the first investigation of agostic interactions through single-crystal EPR spectroscopy. We conclusively show here that the structure and properties of these CoII complexes can be strongly influenced through interactions in the secondary coordination sphere. Additionally, we unravel a unique ligand rearrangement for these classes of anionic mesoionic carbene-based ligands. |
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