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Updated: May 30, 2026
08:15
Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups
Published on: February 11, 2012
A highly distorted open-shell endohedral Zintl cluster: [Mn@Pb12]3-
Binbin Zhou1, Tobias Krämer, Amber L Thompson
1Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.
Inorganic Chemistry
|August 6, 2011
Summary
Researchers synthesized a novel manganese-centered lead cluster anion, [Mn@Pb(12)](3-), revealing significant structural distortions and electron transfer within the cage. This discovery expands understanding of complex inorganic cluster chemistry.
Area of Science:
- Inorganic Chemistry
- Cluster Chemistry
- Materials Science
Background:
- Exploration of polyanionic metal clusters, particularly those involving main group elements like lead.
- Synthesis and characterization of endohedral clusters where a heteroatom is encapsulated within a metallic cage.
- Understanding electronic structure and bonding in low-valent metal clusters.
Purpose of the Study:
- To synthesize and characterize a novel manganese-centered lead cluster.
- To investigate the structural and electronic properties of the [Mn@Pb(12)](3-) cluster.
- To compare the properties of this cluster with known closed-shell analogues.
Main Methods:
- Reaction of K(4)Pb(9) and 2,2,2-crypt with Mn(3)(Mes)(6) in ethylenediamine (en) and tetrahydrofuran (THF).
- Electrospray mass spectrometry (ESI-MS) for species identification.
- Elemental analysis and electron paramagnetic resonance (EPR) for sample characterization.
- Single crystal X-ray diffraction (SCXRD) to analyze crystal structure and disorder.
- Density Functional Theory (DFT) calculations for electronic structure and geometry optimization.
Main Results:
- Successful synthesis of the anionic cluster [Mn@Pb(12)](3-) within the crystal structure [K(2,2,2-crypt)](3)[Mn@Pb(12)]·1.5en.
- ESI-MS confirmed the presence of the cluster anion in the reaction mixture.
- Despite crystallographic challenges, data indicated a highly distorted, expanded endohedral cluster.
- DFT calculations revealed significant electron density transfer from Mn(-I) to the Pb(12) cage, deviating from idealized icosahedral geometry.
Conclusions:
- The study reports the formation and characterization of a unique manganese-centered lead cluster anion.
- The [Mn@Pb(12)](3-) cluster exhibits significant structural distortions and electronic delocalization, differing from closed-shell analogues.
- DFT calculations provide crucial insights into the bonding and electronic structure of this complex inorganic species.
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