Metal as source of chirality in octahedral complexes with tripodal tetradentate ligands
The challenging control of the absolute configuration of chiral-at-metal complexes is efficiently achieved using the tripodal tetradentate ligand L. The optical resolution of rac-[RhCl2(κ4C,N,N′,P–L)] mediated by (S)-α-phenylglycine provides access to enantiopure complexes of general formula [Rh(κ4C...
| Autores: | , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2018 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/186801 |
| Acceso en línea: | http://hdl.handle.net/10261/186801 |
| Access Level: | acceso abierto |
| Sumario: | The challenging control of the absolute configuration of chiral-at-metal complexes is efficiently achieved using the tripodal tetradentate ligand L. The optical resolution of rac-[RhCl2(κ4C,N,N′,P–L)] mediated by (S)-α-phenylglycine provides access to enantiopure complexes of general formula [Rh(κ4C,N,N′,P–L)A(Solv)][SbF6]n that enantioselectively catalyze the Diels–Alder reaction between methacrolein and HCp with enantiomeric ratio of up to >99/1. The nature of the active species, the origin of the enantioselectivity and mechanistic details are disclosed by means of NMR spectroscopy and DFT studies. |
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