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Isomerization-Controlled Proton-Electron Coupling in a π-Planar Metal Complex
Pingping Huang1, Yukihiro Yoshida1, Tokutaro Komatsu2
1Division of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto606-8502, Japan.
Inorganic Chemistry
|January 12, 2023
Summary
This study demonstrates controlling proton-coupled electron transfer (PCET) in platinum complexes via cis-trans isomerization. Geometric changes significantly alter PCET, offering new avenues for catalyst design.
Area of Science:
- Coordination Chemistry
- Catalysis
- Physical Chemistry
Background:
- Proton-coupled electron transfer (PCET) is crucial in biochemistry and electrochemistry.
- Transition-metal complexes are key catalysts for PCET.
- Controlling PCET often involves tuning metal ions and ligands.
Purpose of the Study:
- To investigate the impact of metal-ligand isomerization on PCET in platinum complexes.
- To demonstrate a novel method for controlling PCET through geometric changes.
Main Methods:
- Synthesis and isolation of cis and trans isomers of Pt(itsq)2.
- Characterization using single-crystal X-ray diffraction.
- Computational analysis of electronic structure and protonation effects.
Main Results:
- The cis and trans isomers of Pt(itsq)2 were successfully isolated and characterized.
- Cis-to-trans isomerization was induced by immersion in organic solvents.
- Theoretical calculations revealed significant variations in proton-electron coupling based on geometric configuration.
Conclusions:
- Metal-ligand isomerization provides a new strategy to control PCET.
- The geometric configuration of platinum complexes profoundly influences proton-electron coupling.
- This finding opens possibilities for designing advanced PCET catalysts.
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