Mechanistic elucidation of the role of metal oxidation states in nickel mediated electrocatalytic coupling of benzyl halides

Pradip K. Das; Priyanka Chakraborty; Sandeep Suryabhan Gholap; Théo P. Gonçalves; Changguang Yao; Huaifeng Li; Zhiping Lai; Abdul-Hamid Emwas; Kuo-Wei Huang

Green Synthesis and Catalysis (Nov 2020)

Mechanistic elucidation of the role of metal oxidation states in nickel mediated electrocatalytic coupling of benzyl halides

Pradip K. Das,
Priyanka Chakraborty,
Sandeep Suryabhan Gholap,
Théo P. Gonçalves,
Changguang Yao,
Huaifeng Li,
Zhiping Lai,
Abdul-Hamid Emwas,
Kuo-Wei Huang

Affiliations

Pradip K. Das: Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia; KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia
Priyanka Chakraborty: Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia; KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia
Sandeep Suryabhan Gholap: Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia; KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia
Théo P. Gonçalves: Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia; KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia
Changguang Yao: Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia; KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia
Huaifeng Li: Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia; KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia
Zhiping Lai: Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia; Advanced Membrane and Porous Materials Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia
Abdul-Hamid Emwas: KAUST Core labs, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia
Kuo-Wei Huang: Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia; KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia; Corresponding author. Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia.

Journal volume & issue: Vol. 1, no. 2
pp. 143 – 149

Abstract

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We 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.

Published in Green Synthesis and Catalysis

ISSN: 2666-5549 (Online)
Publisher: KeAi Communications Co. Ltd.
Country of publisher: China
LCC subjects: Technology: Chemical technology; Science: Chemistry: Organic chemistry: Biochemistry
Website: https://www.keaipublishing.com/en/journals/green-synthesis-and-catalysis/

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