Tl since good oxidant used as catalyst (slide1
Tl can be found in the oxidation states of +1 or +3, with Tl+1 more stable due to the inert pair
effect that stabilizes the electrons in the 6s orbital and makes it less likely to participate in
bonding.
Due to this property, Tl (III) can act as a strong oxidizing agent, which is useful in organic
synthesis.
One such example is using thallium chloride as the catalyst for acetylation reactions. Such
reactions are usually slow due to the poor nucleophilic properties of the hydroxyl group that
prevents the addition of acetyl group. The TlCl3 catalyzed benzylic alcohol acetylation under
free solvent conditions can shorten the reaction time to less than 10 minutes, compared to several
hours without the catalyst.
Tl in technology(slide 2
The availability of Tl’s 6p orbitals for bonding enables flexible bonding with ligands, impacting
its optical properties and making it a good semiconductor for radiation detection. Thallium
gallium selenide, a wide-band-gap semiconductor, is used in X-ray and gamma-ray detection.
Its structure consists of [GaSe₂]⁻ layers stacked to form TlGaSe₂, with Tl atoms 6-coordinated
to Se atoms, creating weak bonds between layers.
This semiconductor is a good radiation detector because Tl’s high atomic number (Z) enhances
electron density, improving conductivity and radiation absorption.
As the inert pair effect lowers the energy of Tl's 6p orbitals, strengthening its overlap with Se's
4p orbitals, the bond has more covalent character, leading to delocalized electronic states where
electrons spread across the lattice, which improves the sensitivity and response speed of the
material.
Tl 6p orbitals primarily contribute to the conduction band, while Se 4p orbitals dominate the
valence band. It’s only when electrons gain enough energy that they can jump from the valence
band to the conduction band and conduct electricity. The band gap of over electron volts of this
semiconductor is relatively wide compared to conventional semiconductors. It is wide enough to
reduce the number of thermally excited electrons at room temperature, reducing leakage current,
but still allows electron movement when absorbing high energy photons.
Tl anticancer drugs (slide3
Although thallium is highly toxic, coordinating it with organic molecules reduces its toxicity and
imparts antifungal and antibacterial properties. In 2021, Ghadermazi and colleagues synthesized
a novel thallium complex using pyridine dicarboxylate derivatives.
The complex features a nine-coordinated Tl(III) ion, where three pyridine-2,6-dicarboxylate molecules
coordinate tridentately through two oxygen and one nitrogen. This compound selectively targets
over-proliferating cells, inducing apoptosis by generating reactive oxygen species. The unique
coordination chemistry lowers toxicity and offers potential for further research into its chemical properties
and therapeutic applications.
New research (slide 4
In 2023, Toth and colleagues found a stable red mixed valence thallium(III)-thallium(I) complex.
The element itself is colorless in either oxidation state. Despite the tendency for spontaneous
reduction to Tl(I), this complex can stay stable in dmso for years.
The red complex has several isomers, with the most stable form achieved by coordination of
Tl(III) with the counterion DMSO bridging other Tl ions through two oxygens. The solvent
DMSO seems to have well-tuned reducing and coordination ability to stabilize the mixed valence
structure, reducing electrostatic repulsion between the two oxidation states. And its Sulfur atom
weakly interacts with Tl(I), which adds to the stability. This stable complex shows potential for
future studies, including its use as a strong oxidizing agent in kinetic studies due to the color
change with oxidation state change and possibly in anticancer therapy.
