Synthesis of rare-earth borolide sandwich complexes by multi-electron borole reduction
- 1Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China Xiyuan Avenue 2006 Chengdu 611731 China
- 2Key Laboratory of Bioinorganic and Synthetic Chemistry of the Ministry of Education, School of Chemistry, IGCME, GBRCE for Functional Molecular Engineering, Sun Yat-Sen University Guangzhou 510006 China
- 3Department of Chemistry, School of Life Sciences, University of Sussex Brighton BN1 9QR UK
Abstract
The limited redox chemistry of rare-earth (RE) elements means that multi-electron transfer reactions with RE compounds are a major synthetic challenge. Here, we demonstrate multi-electron reduction of a borole in two complementary RE reaction systems. In the first approach, the dimetallic lanthanum(iii) compound [(η5-C5iPr5)La(µ:η6:η6-C6H6)La(η5-C5iPr5)], containing a benzene tetra-anion ligand, reduces two equivalents of the ferrocenyl–borole FcBC2(SiMe3)2C2Me2 (1) to give the double sandwich complex [{(C5iPr5)RE}FcBC2(SiMe3)2C2Me2] (3-RE, RE = La), containing a 6π-aromatic borolide di-anion. In the second, complementary reaction type, combining KC8 with 1 and the half-sandwich complexes [(C5iPr5)RE(BH4)2(THF)] (RE = Y, La, Dy) also gives 3-RE but with a broader range of rare-earth elements. In 3-RE, evidence for two-electron reduction of the borole is supported by comparisons with the magnesium borolide [Mg(FcBC2(SiMe3)2C2Me2)(THF)3] (2). In contrast, salt-metathesis approaches to 3-RE were ineffective, with alkali metal reduction of the borole proving to be unsuccessful, and 2 does not undergo salt metathesis with rare-earth precursors. The dysprosium analogue 3-Dy exhibits single-molecule magnet behaviour, with an effective barrier of 1222(8) cm−1 and magnetic hysteresis up to 60 K.
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BibTeX
@article{peng2026synthesis,
title = {{Synthesis of rare-earth borolide sandwich complexes by multi-electron borole reduction}},
author = {Xiao-Han Peng and Tao Shang and Yan-Cong Chen and Arpan Mondal and Ming Liu and Yu-Han Du and Ying Liu and Ming-Liang Tong and Richard A. Layfield and Fu-Sheng Guo},
journal = {Chemical Science},
year = {2026},
month = aug,
doi = {10.1039/d6sc05163d},
url = {https://doi.org/10.1039/d6sc05163d},
note = {CC BY 3.0},
}
RIS
TY - JOUR
TI - Synthesis of rare-earth borolide sandwich complexes by multi-electron borole reduction
AU - Xiao-Han Peng
AU - Tao Shang
AU - Yan-Cong Chen
AU - Arpan Mondal
AU - Ming Liu
AU - Yu-Han Du
AU - Ying Liu
AU - Ming-Liang Tong
AU - Richard A. Layfield
AU - Fu-Sheng Guo
PY - 2026
DA - 2026/08/27
JO - Chemical Science
DO - 10.1039/d6sc05163d
UR - https://doi.org/10.1039/d6sc05163d
AB - The limited redox chemistry of rare-earth (RE) elements means that multi-electron transfer reactions with RE compounds are a major synthetic challenge. Here, we demonstrate multi-electron reduction of a borole in two complementary RE reaction systems. In the first approach, the dimetallic lanthanum(iii) compound [(η5-C5iPr5)La(µ:η6:η6-C6H6)La(η5-C5iPr5)], containing a benzene tetra-anion ligand, reduces two equivalents of the ferrocenyl–borole FcBC2(SiMe3)2C2Me2 (1) to give the double sandwich complex [{(C5iPr5)RE}FcBC2(SiMe3)2C2Me2] (3-RE, RE = La), containing a 6π-aromatic borolide di-anion. In the second, complementary reaction type, combining KC8 with 1 and the half-sandwich complexes [(C5iPr5)RE(BH4)2(THF)] (RE = Y, La, Dy) also gives 3-RE but with a broader range of rare-earth elements. In 3-RE, evidence for two-electron reduction of the borole is supported by comparisons with the magnesium borolide [Mg(FcBC2(SiMe3)2C2Me2)(THF)3] (2). In contrast, salt-metathesis approaches to 3-RE were ineffective, with alkali metal reduction of the borole proving to be unsuccessful, and 2 does not undergo salt metathesis with rare-earth precursors. The dysprosium analogue 3-Dy exhibits single-molecule magnet behaviour, with an effective barrier of 1222(8) cm−1 and magnetic hysteresis up to 60 K.
SN - 2041-6520
SN - 2041-6539
ER -