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Theses

Structure of cationic CNHC,Calkyl nickelacycles and their activity in the catalytic functionalization of the C–H bonds of azoles

Abstract : This thesis develops the study of nickel(II) complexes bearing N-heterocyclic carbene ligands (NHC) in two axes: the synthesis and characterization of nickelacyclic complexes with a carbon-carbon chelating ligand (CNHC,Calkyl); and their catalytic activity in the construction of carbon-carbon bonds (Csp2–Csp2/Csp3) of 1-chalcogene-azoles by carbon-hydrogen (C–H) bond functionalization. A series of cationic CNHC,Calkyl-Ni(II) metallacyclic acetonitrile adducts was synthetized by the removal of a cyclopentadienyl ligand from parent 18 valence electron half-sandwich nickelacycles. The cationic complexes were determined to exist as rare coordinatively and electronically unsaturated T-shaped 14 valence electron Ni(II) species, in the solid state. Application of these new complexes to the cross-coupling of benzothiazole with iodoarenes proved to be a successful strategy in Csp2–Csp2 bond formation, by the combination of a stabilizing metallacyclic scaffold with labile ligands. The discovery of a half-sandwich Ni(II)-(NHC)-(benzothiazolyl) species, inactive in the arylation of benzothiazole, but active for the cross-coupling of benzothiazole with iodoalkanes shows the first example of benzothiazole Csp2–Csp3 bond construction with a Ni(II)-NHC catalyst.
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https://tel.archives-ouvertes.fr/tel-02082624
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Bernardo Rosa Lourenço de Pina Cardoso. Structure of cationic CNHC,Calkyl nickelacycles and their activity in the catalytic functionalization of the C–H bonds of azoles. Other. Université de Strasbourg, 2018. English. ⟨NNT : 2018STRAF033⟩. ⟨tel-02082624⟩

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