Geometric Effect in Tetradentate ONNO Nickel(II) Complexes for Coordination‐Induced Spin‐State Switching
Two new square planar ONNO nickel(II) complexes C2_core and C3_core have been synthesized and characterized by single crystal X-ray diffraction, NMR spectroscopy, thermogravimetry, and DFT calculations. The experimental results revealed the effect of the length of diamine bridge in the ligand on the...
| Autores: | , , , , , , |
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| Formato: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2022 |
| País: | España |
| Recursos: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:10256/20710 |
| Acesso em linha: | http://hdl.handle.net/10256/20710 |
| Access Level: | acceso abierto |
| Palavra-chave: | Compostos de níquel -- Reactivitat Reaccions químiques Nickel compounds -- Reactivity Chemical reactions Metalls de transició Transition metals Ciclització (Química) Ring formation (Chemistry) |
| Resumo: | Two new square planar ONNO nickel(II) complexes C2_core and C3_core have been synthesized and characterized by single crystal X-ray diffraction, NMR spectroscopy, thermogravimetry, and DFT calculations. The experimental results revealed the effect of the length of diamine bridge in the ligand on the behavior of the studied complexes in the reaction with N-heterocyclic aromatic amines, while DFT calculations provided a basis for the rationalization of this observation. The complex with propylenediamine bridge (C3_core) readily reacts with pyridine and its derivatives with the formation of high-spin (paramagnetic) complexes with octahedral geometry characterized by X-ray diffraction; electron-donating substituents on the pyridine ring facilitate the coordination of axial ligands. On the contrary, the complex with ethylenediamine bridge (C2_core) does not undergo such a reaction because of the high deformation energy of the core required for the formation of C2_Py complex |
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