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Research Article | Open Access

New deltahedral architectures of rhodium-mediated Pn73− (Pn = Sb and Bi) cages

Lei Qiao, Chuan-Ling Chen, Zhong-Ming Sun ( )
State Key Laboratory of Element-Organic Chemistry, Tianjin Key Lab for Institution Rare Earth Materials and Applications, School of Materials Science and Engineering, Nankai University, Tianjin 300350, China
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Abstract

The reactions of K5Pn4 (Pn = Sb and Bi) and CpRh(PPh3)2 (Cp = C5H5, cyclopentadiene) in ethylenediamine (en) solutions resulted in a series of new Pn73− adducts, {Pn8[Rh(PPh3)]2}2−, {Sb7[Rh(PPh3)]2}2−, and {Sb7[Rh(PPh3)]3}2−, through slight variations in reaction conditions. These clusters represent rare electron-deficient group 15 polyhedral clusters comprising Pn73− with RhPPh3 units in an η5 coordination mode. Notably, the anionic clusters {Sb8[Rh(PPh3)]2}2−, {Sb7[Rh(PPh3)]2}2−, and {Sb7[Rh(PPh3)]3}2− are the first Rh-Sb binary Zintl clusters to date. The synthesis, structure, and bonding of these new deltahedral hybrids were studied for the first time, revealing a highly versatile chemistry associated with classical Pn73− cages and offering a pathway to prepare polyhedral hybrid clusters based on Pn73− cages.

Graphical Abstract

We synthesized a series of heterometallic clusters on the basis of classical Pn73− cages via the reaction of K5Pn4 (Pn = Sb and Bi) with CpRh(PPh3)2 (Cp = C5H5, cyclopentadiene). Density functional theory (DFT) calculations revealed three-center–two-electron (3c–2e) RhPn2 delocalized bonds and weak Rh–Rh interactions for the stabilization of the title clusters. Importantly, this work provides a route to prepare polyhedral hybrid clusters on the basis of Pn73− cages.

Keywords

group 15 clustersheterometallic clustersnanoclusters-based materialselectronic structurescoordination modes

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Nano Research
Volume 18 Issue 3,
March 2025
Article number: 94907253
DOI: 10.26599/NR.2025.94907253

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Cite this article:
Qiao L, Chen C-L, Sun Z-M. New deltahedral architectures of rhodium-mediated Pn73− (Pn = Sb and Bi) cages. Nano Research, 2025, 18(3): 94907253. https://doi.org/10.26599/NR.2025.94907253
Topics:
Antimony compoundsBismuth compoundsCrystal structureQuantum chemistry Synthesis (chemical)

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Received: 21 November 2024
Revised: 01 January 2025
Accepted: 13 January 2025
Published: 19 February 2025
© The Author(s) 2025. Published by Tsinghua University Press.

This is an open access article under the terms of the Creative Commons Attribution 4.0 International License (CC BY 4.0, https://creativecommons.org/licenses/by/4.0/).