NO • Disproportionation by a {RhNO} 9 Pincer-Type Complex
The reactivity of the {RhNO}9 complex [Rh(PCPtBu)(NO)] (1) with NO was studied. A disproportionation reaction takes place in which N2O is released quantitatively, while the complex Rh(PCPtBu)(NO)(NO2) (2), with coordinated nitrite, is formed. The new complex 2 was fully characterized by multinuclear...
| Autores: | , , , |
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| Formato: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2017 |
| País: | Argentina |
| Recursos: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/42223 |
| Acesso em linha: | http://hdl.handle.net/11336/42223 |
| Access Level: | acceso abierto |
| Palavra-chave: | NITROSYL NO? DESPROPORCION NITRO LIGAND PINCER-TYPE LIGAND https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| Resumo: | The reactivity of the {RhNO}9 complex [Rh(PCPtBu)(NO)] (1) with NO was studied. A disproportionation reaction takes place in which N2O is released quantitatively, while the complex Rh(PCPtBu)(NO)(NO2) (2), with coordinated nitrite, is formed. The new complex 2 was fully characterized by multinuclear NMR techniques, IR and X-ray diffraction. The X-ray structure reveals a square pyramidal geometry with an N-bound nitro ligand trans to the Cipso of the PCP ligand and a bent nitrosyl ligand in the apical position. IR measurement of released N2O confirms that one equivalent forms for each molecule of 1. Infrared spectroscopic experiments with 1-15NO and 14NO suggest that the reaction occurs through the intermediacy of a dinitrosyl complex. In addition, DFT calculations were performed to provide more evidence on the structure of the intermediates and to support the observed reactivity. |
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