Electrochemistry and electrocatalysis of H2 generation using hexacoordinated nickel—based complexes

Shotonwa, Ibukun O.; Ejeromedoghene, Onome; Adesoji, Adedoyin Oluseyi; Adewuyi, Sheriff

doi:10.1016/j.catcom.2023.106680

Cited by 3 publications

(1 citation statement)

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“…This catalytic response is due to H 2 evolution and we note that many Ni catalysts are known to be active electrocatalysts for this reaction (Figure S60). − …”

Section: Resultsmentioning

confidence: 99%

Electrocatalytic Semihydrogenation of Terminal Alkynes Using Ligand-Based Transfer of Protons and Electrons

Czaikowski,

Anferov,

Tascher

et al. 2024

J. Am. Chem. Soc.

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Alkyne semihydrogenation is a broadly important transformation in chemical synthesis. Here, we introduce an electrochemical method for the selective semihydrogenation of terminal alkynes using a dihydrazonopyrrole Ni complex capable of storing an H 2 equivalent (2H + + 2e − ) on the ligand backbone. This method is chemoselective for the semihydrogenation of terminal alkynes over internal alkynes or alkenes. Mechanistic studies reveal that the transformation is concerted and Zselective. Calculations support a ligand-based hydrogen-atom transfer pathway instead of a hydride mechanism, which is commonly invoked for transition metal hydrogenation catalysts. The synthesis of the proposed intermediates demonstrates that the catalytic mechanism proceeds through a reduced formal Ni(I) species. The high yields for terminal alkene products without over-reduction or oligomerization are among the best reported for any homogeneous catalyst. Furthermore, the metal−ligand cooperative hydrogen transfer enabled with this system directs the efficient flow of H atom equivalents toward alkyne reduction rather than hydrogen evolution, providing a blueprint for applying similar strategies toward a wide range of electroreductive transformations.

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“…This catalytic response is due to H 2 evolution and we note that many Ni catalysts are known to be active electrocatalysts for this reaction (Figure S60). − …”

Section: Resultsmentioning

confidence: 99%