Involvement of an acetato ligand in the reductive elimination step of the rhodium-catalyzed methanol carbonylation - Archive ouverte HAL Accéder directement au contenu
Chapitre D'ouvrage Année : 2014

Involvement of an acetato ligand in the reductive elimination step of the rhodium-catalyzed methanol carbonylation

Résumé

the complex cis-[PPN][RhI2(CO)2] 1 is produced in high yield by reaction under CO of RhI3 in DMF at 160°C, followed by metathesis of the [NH2Me2]+ with bis(triphenylphosphoranylidene)ammonium]chloride, ([PPN]Cl). Under CO, complex 1 reacts in neat CH3I to afford [PPN][RhI3(COMe)(CO)2] 2. At low water content the reductive elimination reaction was shown by Infrared, 1H and 13C NMR, kinetics measurements and DFT calculations to involve two steps: the substitution of an iodo ligand by an acetate ligand followed by the reductive elimination of acetic anhydride from the [PPN][RhI2(COMe)(OCOMe)(CO)2] 3 intermediate regenerate 1.
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Dates et versions

hal-02042504 , version 1 (20-02-2019)

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  • HAL Id : hal-02042504 , version 1

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Duc Hanh Nguyen, Nicolas Lassauque, T. Davin, Laurent Maron, Carole Le Berre, et al.. Involvement of an acetato ligand in the reductive elimination step of the rhodium-catalyzed methanol carbonylation. Plombeiro, A.J.L. Advances in Organometallic Chemistry and Catalysis: The Silver/Gold Jubilee International Conference on Organometallic Chemistry Celebratory Book, 20, John Wiley & Sons, Inc., pp.259-268, 2014, 978-1-118-74295-2. ⟨hal-02042504⟩
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