Mechanistic elucidation of the role of metal oxidation states in nickel mediated electrocatalytic coupling of benzyl halides
AuthorsDas, Pradip K.
Gholap, Sandeep Suryabhan
Emwas, Abdul-Hamid M.
KAUST DepartmentAdvanced Membranes and Porous Materials Research Center
Biological and Environmental Science and Engineering (BESE) Division
Chemical Engineering Program
Chemical Science Program
Homogeneous Catalysis Laboratory (HCL)
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Permanent link to this recordhttp://hdl.handle.net/10754/667429
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AbstractWe present the mechanistic understanding of an electrochemically-driven nickel-catalyzed coupling reaction. Computational analysis reveals that the spin density is mostly residing on the nickel (Ni) center when NiII is reduced to NiI. Ni-mediated halogen atom abstraction through outer-sphere electron-transfer pathway to yield coupling products under mild conditions is demonstrated. Importantly, we have elucidated the role of NiI and Ni0 for successive coupling of benzyl bromide and benzyl chloride derivatives, respectively, to corresponding bibenzyl products. The Ni-catalyst bearing a PN3P-ligand is an effective catalyst, producing a strong ligand effect on the reactivity and selectivity for the homocoupling reactions.
CitationDas, P. K., Chakraborty, P., Gholap, S. S., Gonçalves, T. P., Yao, C., Li, H., … Huang, K.-W. (2020). Mechanistic elucidation of the role of metal oxidation states in nickel mediated electrocatalytic coupling of benzyl halides. Green Synthesis and Catalysis, 1(2), 143–149. doi:10.1016/j.gresc.2020.10.001
SponsorsWe acknowledge the generous financial support from King Abdullah University of Science and Technology (KAUST).
JournalGreen Synthesis and Catalysis
Except where otherwise noted, this item's license is described as This is an open access article under the CC BY NC-ND license.