Reduction of Li+ within a Borate Anion

Haokun Li; Jiachen Yao; Gan Xu; Shek-Man Yiu; Chi-Kit Siu; Zhen Wang; Yung-Kang Peng; Yi Xie; Ying Wang; Zhenpin Lu

doi:10.1038/s41467-024-46948-8

Reduction of Li⁺within a Borate Anion

Haokun Li, Jiachen Yao, Gan Xu, Shek-Man Yiu, Chi-Kit Siu, Zhen Wang, Yung-Kang Peng, Yi Xie, Ying Wang, Zhenpin Lu^*

^*Corresponding author for this work

Department of Chemistry

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

4 Citations (Scopus)

26 Downloads (CityUHK Scholars)

Abstract

Group 1 elements exhibit the lowest electronegativity values in the Periodic Table. The chemical reduction of Group 1 metal cations M⁺ to M(0) is extremely challenging. Common tetraaryl borates demonstrate limited redox properties and are prone to decomposition upon oxidation. In this study, by employing simple yet versatile bipyridines as ligands, we synthesized a series of redox-active borate anions characterized by NMR and X-ray single-crystal diffraction. Notably, the borate anion can realize the reduction of Li⁺, generating elemental lithium metal and boron radical, thereby demonstrating its potent reducing ability. Furthermore, it can serve as a powerful two-electron-reducing reagent and be readily applied in various reductive homo-coupling reactions and Birch reduction of acridine. Additionally, this borate anion demonstrates its catalytic ability in the selective two-electron reduction of CO₂ into CO.

© The Author(s) 2024

Original language	English
Article number	2590
Number of pages	8
Journal	Nature Communications
Volume	15
Online published	22 Mar 2024
DOIs	https://doi.org/10.1038/s41467-024-46948-8
Publication status	Published - 2024

Funding

This work was supported by grants from the Research Grants Council of The Hong Kong Special Administration Region (Project Nos. CityU 14303621 and 21310922) and start-up funds from the City University of Hong Kong (CityU). Z.L. thanks Prof. Huadong Wang (at Fudan University) and Prof. Zuowei Xie (at Southern University of Science and Technology) for their insightful discussions. C.K.S. thanks CityU for financial support (Project No. 7006003). The high-performance computing clusters of CityU (“CityU Burgundy”) are acknowledged.

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This full text is made available under CC-BY 4.0. https://creativecommons.org/licenses/by/4.0/

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title = "Reduction of Li+ within a Borate Anion",

abstract = "Group 1 elements exhibit the lowest electronegativity values in the Periodic Table. The chemical reduction of Group 1 metal cations M+ to M(0) is extremely challenging. Common tetraaryl borates demonstrate limited redox properties and are prone to decomposition upon oxidation. In this study, by employing simple yet versatile bipyridines as ligands, we synthesized a series of redox-active borate anions characterized by NMR and X-ray single-crystal diffraction. Notably, the borate anion can realize the reduction of Li+, generating elemental lithium metal and boron radical, thereby demonstrating its potent reducing ability. Furthermore, it can serve as a powerful two-electron-reducing reagent and be readily applied in various reductive homo-coupling reactions and Birch reduction of acridine. Additionally, this borate anion demonstrates its catalytic ability in the selective two-electron reduction of CO2 into CO.{\textcopyright} The Author(s) 2024",

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AU - Li, Haokun

AU - Yao, Jiachen

AU - Xu, Gan

AU - Yiu, Shek-Man

AU - Siu, Chi-Kit

AU - Wang, Zhen

AU - Peng, Yung-Kang

AU - Xie, Yi

AU - Wang, Ying

AU - Lu, Zhenpin

PY - 2024

Y1 - 2024

N2 - Group 1 elements exhibit the lowest electronegativity values in the Periodic Table. The chemical reduction of Group 1 metal cations M+ to M(0) is extremely challenging. Common tetraaryl borates demonstrate limited redox properties and are prone to decomposition upon oxidation. In this study, by employing simple yet versatile bipyridines as ligands, we synthesized a series of redox-active borate anions characterized by NMR and X-ray single-crystal diffraction. Notably, the borate anion can realize the reduction of Li+, generating elemental lithium metal and boron radical, thereby demonstrating its potent reducing ability. Furthermore, it can serve as a powerful two-electron-reducing reagent and be readily applied in various reductive homo-coupling reactions and Birch reduction of acridine. Additionally, this borate anion demonstrates its catalytic ability in the selective two-electron reduction of CO2 into CO.© The Author(s) 2024

AB - Group 1 elements exhibit the lowest electronegativity values in the Periodic Table. The chemical reduction of Group 1 metal cations M+ to M(0) is extremely challenging. Common tetraaryl borates demonstrate limited redox properties and are prone to decomposition upon oxidation. In this study, by employing simple yet versatile bipyridines as ligands, we synthesized a series of redox-active borate anions characterized by NMR and X-ray single-crystal diffraction. Notably, the borate anion can realize the reduction of Li+, generating elemental lithium metal and boron radical, thereby demonstrating its potent reducing ability. Furthermore, it can serve as a powerful two-electron-reducing reagent and be readily applied in various reductive homo-coupling reactions and Birch reduction of acridine. Additionally, this borate anion demonstrates its catalytic ability in the selective two-electron reduction of CO2 into CO.© The Author(s) 2024

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Reduction of Li⁺within a Borate Anion

Abstract

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ECS: Synthesis, Structure and Reactivity of Two-coordinate Boron Cations, Boron Radicals and Boryl Anions

GRF: Synthesis, Structure and Reaction Chemistry of Carborane-fused Boracycles Bearing Electron-precise B-B Single Bond(s)

Cite this

Reduction of Li+ within a Borate Anion

Abstract

Funding

Publisher's Copyright Statement

RGC Funding Information

UN SDGs

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Other Access Options

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Projects

ECS: Synthesis, Structure and Reactivity of Two-coordinate Boron Cations, Boron Radicals and Boryl Anions

GRF: Synthesis, Structure and Reaction Chemistry of Carborane-fused Boracycles Bearing Electron-precise B-B Single Bond(s)

Cite this

Reduction of Li⁺within a Borate Anion