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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Alkyl carbon-nitrogen reductive elimination from platinum(IV)-sulfonamide complexes
Andrew V Pawlikowski1, April D Getty, Karen I Goldberg
1Department of Chemistry, University of Washington, PO Box 351700, Seattle, Washington 98195-1700, USA.
Platinum(IV) complexes with sulfonamide ligands undergo selective C-N or C-C bond formation via reductive elimination. Reaction conditions and solvent control the selectivity, enabling targeted synthesis of N-methylsulfonamides or ethane.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Synthetic Chemistry
Background:
- Platinum(IV) complexes are versatile precursors in organometallic chemistry.
- Sulfonamide ligands offer unique electronic and steric properties.
- Understanding reductive elimination pathways is crucial for catalytic applications.
Purpose of the Study:
- To synthesize and characterize novel Platinum(IV) complexes with monodentate sulfonamide ligands.
- To investigate the thermal reactivity and reductive elimination pathways of these complexes.
- To explore methods for controlling selectivity in C-N and C-C bond formation.
Main Methods:
- Synthesis of Platinum(IV) complexes fac-(dppbz)PtMe(3)(NHSO(2)R).
- Thermolysis experiments in various solvents (benzene-d(6), nitrobenzene-d(5)).
- Mechanistic studies involving sulfonamide anions and spectroscopic analysis.
Main Results:
- Compounds 1a-c exhibit competitive C-N and C-C reductive elimination.
- Reaction conditions (solvent, presence of anion) dictate selectivity.
- High yields of C-N coupled products achieved in benzene-d(6) with sulfonamide anions.
- Exclusive C-C reductive elimination observed in nitrobenzene-d(5).
Conclusions:
- Selective C-N or C-C bond formation from Platinum(IV) complexes is achievable.
- Solvent and the presence of sulfonamide anions are key factors in controlling selectivity.
- A two-step mechanism involving ligand dissociation and nucleophilic attack explains the observed reactivity.
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