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; Theo Goncalves; Changguang Yao; Huaifeng Li; Zhiping Lai; Abdul-Hamid M. Emwas; Kuo-Wei Huang

doi:10.1016/j.gresc.2020.10.001

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, Theo Goncalves, Changguang Yao, Huaifeng Li, Zhiping Lai, Abdul-Hamid M. Emwas, Kuo-Wei Huang

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	143-149
Number of pages	7
Journal	Green Synthesis and Catalysis
Volume	1
Issue number	2
DOIs	https://doi.org/10.1016/j.gresc.2020.10.001
State	Published - Nov 2020

Access to Document

10.1016/j.gresc.2020.10.001

https://repository.kaust.edu.sa/bitstream/10754/667429/1/1-s2.0-S2666554920300314-main.pdf

Cite this

@article{ee5c2f21e0ee46ffbe6334bc49434d89,

title = "Mechanistic elucidation of the role of metal oxidation states in nickel mediated electrocatalytic coupling of benzyl halides",

abstract = "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.",

author = "Das, {Pradip K.} and Priyanka Chakraborty and Gholap, {Sandeep Suryabhan} and Theo Goncalves and Changguang Yao and Huaifeng Li and Zhiping Lai and Emwas, {Abdul-Hamid M.} and Kuo-Wei Huang",

note = "KAUST Repository Item: Exported on 2021-02-16 Acknowledgements: We acknowledge the generous financial support from King Abdullah University of Science and Technology (KAUST).",

year = "2020",

month = nov,

doi = "10.1016/j.gresc.2020.10.001",

language = "English (US)",

volume = "1",

pages = "143--149",

journal = "Green Synthesis and Catalysis",

issn = "2666-5549",

publisher = "KeAi Communications Co",

number = "2",

}

TY - JOUR

T1 - Mechanistic elucidation of the role of metal oxidation states in nickel mediated electrocatalytic coupling of benzyl halides

AU - Das, Pradip K.

AU - Chakraborty, Priyanka

AU - Gholap, Sandeep Suryabhan

AU - Goncalves, Theo

AU - Yao, Changguang

AU - Li, Huaifeng

AU - Lai, Zhiping

AU - Emwas, Abdul-Hamid M.

AU - Huang, Kuo-Wei

N1 - KAUST Repository Item: Exported on 2021-02-16 Acknowledgements: We acknowledge the generous financial support from King Abdullah University of Science and Technology (KAUST).

PY - 2020/11

Y1 - 2020/11

N2 - 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.

AB - 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.

UR - http://hdl.handle.net/10754/667429

UR - https://linkinghub.elsevier.com/retrieve/pii/S2666554920300314

U2 - 10.1016/j.gresc.2020.10.001

DO - 10.1016/j.gresc.2020.10.001

M3 - Article

SN - 2666-5549

VL - 1

SP - 143

EP - 149

JO - Green Synthesis and Catalysis

JF - Green Synthesis and Catalysis

IS - 2

ER -

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

Abstract

Access to Document

Other files and links

Fingerprint

Cite this