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Compounds with the electron-rich [W6Cl18]2- cluster anion
Sonja Tragl1, Markus Ströbele, Jochen Glaser
1Institut für Anorganische Chemie, Universität Tübingen, Ob dem Himmelreich 7, D-72074 Tübingen, Germany.
Inorganic Chemistry
|April 14, 2009
Summary
New tungsten-based cluster compounds with 20 electrons, exceeding the typical 16, were synthesized. These compounds, featuring the [W(6)Cl(18)](2-) anion, demonstrate stability in solution and act as mild oxidizing agents.
Area of Science:
- Inorganic Chemistry
- Materials Science
- Cluster Chemistry
Background:
- Octahedral M(6)X(12) clusters typically contain 16 cluster electrons.
- Tungsten-based clusters offer unique electronic and structural properties.
- Understanding cluster electron counts is crucial for predicting reactivity.
Purpose of the Study:
- To synthesize and characterize novel tungsten cluster compounds of the formula A(2)[W(6)Cl(18)].
- To investigate the structural trends influenced by various singly charged cations (A).
- To explore the electronic properties and redox behavior of the [W(6)Cl(18)](2-) cluster.
Main Methods:
- Synthesis of A(2)[W(6)Cl(18)] compounds via reduction of W(6)Cl(18).
- Characterization using Electrospray Ionization (ESI) mass spectrometry.
- Electrochemical analysis via cyclic voltammetry.
Main Results:
- Successful synthesis of A(2)[W(6)Cl(18)] clusters with diverse cations (K, Rb, Ag, Tl, NH4, etc.).
- Evidence of 20 cluster electrons in an octahedral M(6)X(12) type cluster, exceeding the conventional 16-electron rule.
- ESI mass spectra and cyclic voltammetry confirm the stability of the [W(6)Cl(18)](2-) unit and its mild oxidizing capability.
Conclusions:
- The [W(6)Cl(18)](2-) cluster unit is stable in solution and exhibits a 20-electron configuration.
- Neutral W(6)Cl(18) is a mild oxidizing agent due to its propensity for two-electron reduction.
- Systematic structural investigations are enabled by the series of synthesized ionic clusters.
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