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Electrocatalytic Proton Reduction by a Cobalt Complex Containing a Proton Responsive Bis(alkylimdazole)methane Ligand: Involvement of a C–H Bond in H2 Formation

Abstract : Homogeneous electrocatalytic proton reduction is reported using cobalt complex [ 1 ](BF 4 ) 2 . This complex comprises two bis(1‐methyl‐4,5‐diphenyl‐1H‐imidazol‐2‐yl)methane (HBMIM Ph2 ) ligands that contain an acidic methylene moiety in their backbone. Upon reduction of [ 1 ](BF 4 ) 2 by either electrochemical or chemical means, one of its HBMIM Ph2 ligands undergoes deprotonation under the formation of dihydrogen. Addition of a mild proton source (acetic acid) to deprotonated complex [ 2 ](BF 4 ) regenerates protonated complex [ 1 ](BF 4 ) 2 . In presence of acetic acid in acetonitrile solvent [ 1 ](BF 4 ) 2 shows electrocatalytic proton reduction with a k obs of ~200 s ‐1 at an overpotential of 590 mV. Mechanistic investigations supported by Density Functional Theory (BP86) reveal that dihydrogen formation takes place in an intramolecular fashion through the participation of a methylene C–H bond of the HBMIM Ph2 ligand and a Co II –H bond through formal heterolytic splitting of the latter. These results represent the joint involvement of a base metal‐hydride and a C–H bond in electrocatalytic proton reduction and are of interest to the development of responsive ligands for molecular (base)metal (electro)catalysis.
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https://hal.univ-brest.fr/hal-02564719
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Submitted on : Tuesday, May 5, 2020 - 11:37:24 PM
Last modification on : Wednesday, May 6, 2020 - 1:42:23 AM

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Pradip Ghosh, Sander de Vos, Martin Lutz, Frederic Gloaguen, Philippe Schollhammer, et al.. Electrocatalytic Proton Reduction by a Cobalt Complex Containing a Proton Responsive Bis(alkylimdazole)methane Ligand: Involvement of a C–H Bond in H2 Formation. Chemistry - A European Journal, Wiley-VCH Verlag, 2020, ⟨10.1002/chem.201905746⟩. ⟨hal-02564719⟩

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