Citation: Ya-Nan Yang, Zi-Sheng Li, Sourav Mondal, Lei Qiao, Cui-Cui Wang, Wen-Juan Tian, Zhong-Ming Sun, John E. McGrady. Metal-metal bonds in Zintl clusters: Synthesis, structure and bonding in [Fe₂Sn₄Bi₈]^3– and [Cr₂Sb₁₂]^3–[J]. Chinese Chemical Letters, ;2024, 35(8): 109048. doi: 10.1016/j.cclet.2023.109048 shu

Metal-metal bonds in Zintl clusters: Synthesis, structure and bonding in [Fe₂Sn₄Bi₈]^3– and [Cr₂Sb₁₂]^3–

Ya-Nan Yang ^{a, 1} ,
Zi-Sheng Li ^{b, 1} ,
Sourav Mondal ^b ,
Lei Qiao ^a ,
Cui-Cui Wang ^a ,
Wen-Juan Tian ^a ,
Zhong-Ming Sun ^{a, *,} ,
John E. McGrady ^{b, *,}

a.
State Key Laboratory of Element-Organic Chemistry, Tianjin Key Lab for Rare Earth Materials and Applications, School of Materials Science and Engineering, Nankai University, Tianjin 300350, China
b.
Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, Oxford, OX1 3QR, United Kingdom

sunlab@nankai.edu.cn

john.mcgrady@chem.ox.ac.uk

Received Date: 8 August 2023
Revised Date: 29 August 2023
Accepted Date: 3 September 2023
Available Online: 7 September 2023

Figures(10)

We report here the synthesis and characterization of two new members of the M₂E₁₂ family of endohedral Zintl clusters, [Fe₂Sn₄Bi₈]^3– and [Cr₂Sb₁₂]^3–, both of which contain open-shell metal dimers encapsulated inside a triple-decker cluster of main-group atoms. The 75-electron [Fe₂Sn₄Bi₈]^3– cluster has a D_4h-symmetric structure, while [Cr₂Sb₁₂]^3–, despite having the same 75-electron count, is strongly distorted to a geometry that resembles a CrSb₈ crown capped by a CrSb₄ unit. The structural differences between the two are driven by the increasing availability of 3d electron density in the earlier transition metal, which leads, ultimately, to different electronic configurations in the two clusters. The trends precisely mirror those observed in the ME₁₀ and ME₁₂ families containing a single transition metal ion.
- Zintl anions,
- Endohedral clusters,
- Metal-metal bond,
- Second-order Jahn-Teller effect,
- DFT calculation
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Metal-metal bonds in Zintl clusters: Synthesis, structure and bonding in [Fe₂Sn₄Bi₈]^3– and [Cr₂Sb₁₂]^3–