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-[RhCl(κC,N,N′,P-L)] mediated by (S)-α-phenylglycine provides access to enantiopure complexes of general formula [Rh(κC,N,...

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Detalles Bibliográficos
Publicado en:	Journal of the American Chemical Society Vol. 140; no. 3; pp. 912 - 916
Autores principales:	Carmona, María, Rodríguez, Ricardo, Passarelli, Vincenzo, Lahoz, Fernando J., García-Orduña, Pilar, Carmona, Daniel
Formato:	Artículo
Publicado:	American Chemical Society 1/24/2018
Materias:	Metal complexes Chirality Nuclear magnetic resonance spectroscopy Density functional theory Enantioselective catalysis Ligand analysis
Acceso en línea:	Ver este registro en EBSCOhost

Descripción
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-[RhCl(κC,N,N′,P-L)] mediated by (S)-α-phenylglycine provides access to enantiopure complexes of general formula [Rh(κC,N,N′,P-L)A- (Solv)][SbF] 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.