Mechanistic insights of the Ir‐bipyridonate catalyzed aqueous methanol dehydrogenation and transfer dehydrogenation to acetophenone: Experimental and DFT study - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue European Journal of Inorganic Chemistry Année : 2024

Mechanistic insights of the Ir‐bipyridonate catalyzed aqueous methanol dehydrogenation and transfer dehydrogenation to acetophenone: Experimental and DFT study

Résumé

The mechanisms of the Cp*IrIII(bpyOO)‐catalyzed (bpyOO = bidentate (NN) doubly deprotonated 2,2'‐bipyridine‐6,6'‐diol) acceptorless methanol dehydrogenation and acetophenone transfer hydrogenation by methanol under basic conditions have been explored by the combination of 1H NMR, kinetics, and DFT computational studies. During dehydrogenation of methanol and its dehydrogenated derivatives, the presence of two iridium hydride species (anionic [Cp*Ir(bpyOO)H]‐, C* and neutral [Cp*Ir(bpyOOH)H], D*), which interconvert depending on pH, was detected. The DFT studies on a Cp model system highlighted three interrelated catalytic cycles of methanol, formaldehyde and formic acid dehydrogenation, all leading to the same hydride intermediates C and D. The dehydrogenation of methanol prefers a direct β‐hydride transfer pathway from the methoxide ion to Ir, rather than the classical β‐hydride elimination pathway from a coordinated methoxide ligand, but an alternative bifunctional H+/H‐ transfer with involvement of a ligand O atom may become competitive at lower pH. The transfer hydrogenation of acetophenone using methanol as hydrogen source features species C* as resting state, with the acetophenone reduction being rate‐determining and following the reverse pathway of methanol oxidation, with a first‐order acetophenone decay and a kinetic isotope effect of 2.36±0.09.
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Licence : CC BY NC ND - Paternité - Pas d'utilisation commerciale - Pas de modification

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hal-04502966 , version 1 (27-03-2024)

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Paternité - Pas d'utilisation commerciale - Pas de modification

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Nidhi Garg, Rinaldo Poli, Basker Sundararaju. Mechanistic insights of the Ir‐bipyridonate catalyzed aqueous methanol dehydrogenation and transfer dehydrogenation to acetophenone: Experimental and DFT study. European Journal of Inorganic Chemistry, In press, ⟨10.1002/ejic.202300744⟩. ⟨hal-04502966⟩
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