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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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:
Acceso en línea:Ver este registro en EBSCOhost
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      pub: American Chemical Society
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        10.1021/jacs.7b12731
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        atl: Metal as Source of Chirality in Octahedral Complexes with Tripodal Tetradentate Ligands.
      aug:
        au:
          Carmona, María
          Rodríguez, Ricardo
          Passarelli, Vincenzo
          Lahoz, Fernando J.
          García-Orduña, Pilar
          Carmona, Daniel
        affil:
          Departamento de Química Inorgánica, Instituto de Síntesis Química y Cataálisis Homogeénea (ISQCH), CSIC - Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain
          Centro Universitario de la Defensa, Ctra. Huesca s/n, 50090 Zaragoza, Spain
      su:
        Metal complexes
        Chirality
        Nuclear magnetic resonance spectroscopy
        Density functional theory
        Enantioselective catalysis
        Ligand analysis
      sug:
        subj:
          Metal complexes
          Chirality
          Nuclear magnetic resonance spectroscopy
          Density functional theory
          Enantioselective catalysis
          Ligand analysis
      ab: 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.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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          year: 2018
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