Piano-stool d(6)-rhodium(III) complexes of chelating pyridine-based ligands and their papain bioconjugates for the catalysis of transfer hydrogenation of aryl ketones in aqueous medium - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Molecular Catalysis B: Enzymatic Année : 2015

Piano-stool d(6)-rhodium(III) complexes of chelating pyridine-based ligands and their papain bioconjugates for the catalysis of transfer hydrogenation of aryl ketones in aqueous medium

Nathalie Madern
  • Fonction : Auteur
Alice Chevalley
  • Fonction : Auteur
Orazio Nicolotti
  • Fonction : Auteur
Ilaria Ciofini
Giuseppe Felice Mangiatordi
  • Fonction : Auteur
Michèle Salmain

Résumé

Two half-sandwich d6-rhodium(III) complexes of the general formula [(η5-Cp*)Rh(N^N)Cl]Cl where N^N is a phenanthroline or a bispyridine methane derivative carrying a thiol-targeting maleimide or chloroacetamide function were synthesized and characterized. Both complexes were able to catalyse the transfer hydrogenation of 2,2,2-trifluoroacetophenone in aqueous medium using formate or phosphite as hydrogen donor. Covalent anchoring of these complexes to the cysteine endoproteinase papain yielded hybrid metalloproteins with transfer hydrogenase properties. Under optimized conditions of pH, hydrogen donor concentration and catalyst load, conversion of substrate was nearly quantitative within 24 h at 40 °C and the (S)-enantiomer was obtained preferably albeit with a modest enantiomeric excess of 710%. Covalent docking simulations complemented the experimental findings suggesting a molecular rationale for the observed low enantioselectivity. The harmonious use of experimental and theoretical approaches represents an unprecedented starting point for driving the rational design of artificial metalloenzymes built up from papain with higher catalytic efficiency.
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Dates et versions

hal-01480764 , version 1 (01-03-2017)

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Nathalie Madern, Nicolas Queyriaux, Alice Chevalley, Mahsa Ghasemi, Orazio Nicolotti, et al.. Piano-stool d(6)-rhodium(III) complexes of chelating pyridine-based ligands and their papain bioconjugates for the catalysis of transfer hydrogenation of aryl ketones in aqueous medium. Journal of Molecular Catalysis B: Enzymatic, 2015, 122, pp.314-322. ⟨10.1016/j.molcatb.2015.10.007⟩. ⟨hal-01480764⟩
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