Half‐Sandwich Nickel(II) NHC‐Picolyl Complexes as Catalysts for the Hydrosilylation of Carbonyl Compounds: Evidence for NHC‐Nickel Nanoparticles under Harsh Reaction Conditions
| Autor: | Vasiliki Papaefthimiou, Thierry Romero, Vincent Ritleng, Franck Ulm, Saurabh Shahane, Cuong Pham-Huu, Lai Truong-Phuoc, Matthieu Chessé, Michael J. Chetcuti, Christophe Michon |
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| Přispěvatelé: | Laboratoire d'innovation moléculaire et applications (LIMA), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry Hydrosilylation [CHIM.ORGA]Chemical Sciences/Organic chemistry Nickelocene chemistry.chemical_element [CHIM.CATA]Chemical Sciences/Catalysis 010402 general chemistry 01 natural sciences Aldehyde 0104 chemical sciences Catalysis Inorganic Chemistry chemistry.chemical_compound Nickel chemistry Bromide Hemilability Polymer chemistry [CHIM.COOR]Chemical Sciences/Coordination chemistry Carbene |
| Zdroj: | European Journal of Inorganic Chemistry European Journal of Inorganic Chemistry, Wiley-VCH Verlag, In press, 2021 (30), pp.3074-3082. ⟨10.1002/ejic.202100371⟩ |
| ISSN: | 1434-1948 1099-0682 |
| DOI: | 10.1002/ejic.202100371⟩ |
| Popis: | International audience; The cationic [NiCp(Mes-NHC-CH2py]Br complex 2 a was prepared directly by the reaction of nickelocene with 1-(2-picolyl)-3-mesityl-imidazolium bromide (1), and its PF6− derivative 2 b, by subsequent salt metathesis. X-ray diffraction studies and Variable Temperature 1H NMR experiments run with 2 a and 2 b strongly suggest the bidentate coordination of the picolyl-functionalized carbene to the nickel both in the solid state and in solution in both cases. These data suggest the absence of hemilabile behavior of the latter, even in the presence of a coordinating anion. Both complexes show similar activity in aldehyde hydrosilylation, further implying the absence of hemilability of the picolyl-functionalized carbene, and effectively reduce a broad scope of aldehydes in the absence of additive under mild conditions. In the case of ketones, effective hydrosilylation is only observed in the presence of a catalytic amount of potassium t-butoxide at 100 °C. Dynamic light scattering, scanning transmission electron microscopy and X-ray photoelectron spectroscopy show evidence for the involvement of NHC-picolyl-Ni nanoparticles under these conditions. |
| Databáze: | OpenAIRE |
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