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Updated: Aug 9, 2025
07:20
Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
14.0K
Square-Planar Anionic Pt0 Complexes
Hajime Kameo1, Yudai Tanaka1, Yoshihiro Shimoyama2
1Department of Chemistry, Graduate School of Science, Osaka Metropolitan University Gakuen-cho, Naka-ku, Sakai, Osaka, 599-8531, Japan.
Angewandte Chemie (International Ed. in English)
|February 22, 2023
Summary
Researchers synthesized a novel T-shaped platinum(0) complex. This platinum complex, stabilized by a diphosphine-borane ligand, allows for the isolation of anionic platinum(0) complexes for the first time.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Materials Science
Background:
- Electron-rich metal complexes are often unstable and difficult to isolate.
- Stabilizing unusual oxidation states and geometries in metal complexes is a key challenge in chemistry.
Purpose of the Study:
- To synthesize and characterize a novel T-shaped platinum(0) complex.
- To investigate the stabilizing effect of a diphosphine-borane ligand on platinum(0).
- To explore the formation and structural authentication of anionic platinum(0) complexes.
Main Methods:
- Synthesis of a T-shaped platinum(0) complex featuring a diphosphine-borane ligand.
- Reaction with Lewis bases to form tetracoordinate complexes.
- Isolation and structural characterization of anionic platinum(0) complexes using X-ray diffraction.
- Determination of oxidation state and electronic configuration via X-ray photoelectron spectroscopy and DFT calculations.
Main Results:
- A T-shaped Pt(0) complex with a diphosphine-borane ligand was successfully prepared.
- The Pt→B interaction enhanced metal electrophilicity, enabling Lewis base addition.
- Anionic Pt(0) complexes, [(DPB)PtX]⁻ (X=CN, Cl, Br, I), were isolated and structurally confirmed as square-planar.
- X-ray photoelectron spectroscopy and DFT calculations confirmed the d¹⁰ configuration and Pt(0) oxidation state.
Conclusions:
- Coordination of Lewis acids as Z-type ligands is an effective strategy for stabilizing electron-rich metal complexes.
- This approach allows for the stabilization and isolation of elusive metal complexes with uncommon geometries.
- The study provides the first structural authentication of anionic Pt(0) complexes.
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