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NCN pincer-Pt complexes coordinated by (nitronyl nitroxide)-2-ide radical anion
Xun Zhang1, Shuichi Suzuki, Masatoshi Kozaki
1Department of Chemistry, Graduate School of Science, Osaka City University, Sugimoto, Sumiyoshi-ku, Osaka 558-8585, Japan.
Journal of the American Chemical Society
|October 19, 2012
Summary
New platinum (Pt) complexes featuring a nitronyl nitroxide radical anion were synthesized. Coordination to platinum shifted the radical anion
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Radical Chemistry
Background:
- Pincer ligands offer unique coordination environments for metal centers.
- Nitronyl nitroxide radicals are versatile paramagnetic building blocks.
- Platinum complexes have diverse applications in catalysis and medicine.
Purpose of the Study:
- To synthesize and characterize novel pincer-platinum complexes incorporating a nitronyl nitroxide radical anion.
- To investigate the structural and electronic effects of coordinating the radical anion to a platinum(II) center.
- To determine the impact of platinum coordination on the redox properties of the nitronyl nitroxide moiety.
Main Methods:
- Synthesis of pincer-Pt complexes via established organometallic procedures.
- Structural elucidation using single-crystal X-ray diffraction.
- Spectroscopic characterization including NMR and EPR spectroscopy.
- Electrochemical studies to determine oxidation potentials.
Main Results:
- Stable pincer-Pt complexes with the nitronyl nitroxide radical anion were prepared in high yields.
- The structures of both the neutral and oxidized Pt complexes were unambiguously confirmed.
- Coordination to Pt(II) resulted in a significant negative shift of approximately 0.6 V in the oxidation potential of the nitronyl nitroxide.
Conclusions:
- The successful synthesis and characterization of these novel complexes demonstrate the feasibility of incorporating radical anions into pincer-platinum frameworks.
- The observed negative shift in oxidation potential highlights the electronic influence of the platinum center on the coordinated radical.
- These findings open avenues for exploring the redox activity and potential applications of such paramagnetic platinum complexes.
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