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...

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Detalhes bibliográficos
Autores: Carmona, María, Rodríguez Martínez, Ricardo, Passarelli, Vincenzo, Lahoz, Fernando J., García-Orduña, Pilar, Carmona, Daniel
Formato: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2018
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/186801
Acesso em linha:http://hdl.handle.net/10261/186801
Access Level:acceso abierto
Descrição
Resumo: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.