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Updated: Jul 17, 2026

Preparation of N-(2-alkoxyvinyl)sulfonamides from N-tosyl-1,2,3-triazoles and Subsequent Conversion to Substituted Phthalans and Phenethylamines
Published on: January 3, 2018
Platinum stilbazoles: ring-walking coupled with aryl-halide bond activation
David Strawser1, Amir Karton, Olena V Zenkina
1Department of Organic Chemistry, Weizmann Institute of Science, Rehovot 76100, Israel.
Platinum complexes with bromophenylpyridine ligands were studied. Heating causes the platinum to move along the pi-system, adding across the carbon-bromine bond via a unimolecular pathway.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Materials Science
Background:
- Tetrakis(triethylphosphine)platinum(0) is a common organometallic precursor.
- 4-[trans-2-(4-bromophenyl)vinyl]pyridine is a functionalized pyridine ligand with a vinyl group.
Purpose of the Study:
- To investigate the reaction between tetrakis(triethylphosphine)platinum(0) and 4-[trans-2-(4-bromophenyl)vinyl]pyridine.
- To characterize the resulting platinum complexes and elucidate the reaction mechanism.
Main Methods:
- Synthesis and full characterization of platinum complexes.
- X-ray crystallography for structural determination.
- Kinetic studies to determine reaction order and mechanism.
- Density functional theory (DFT) calculations to model the reaction pathway.
Main Results:
- The platinum center initially coordinates to the bridging double bond of the ligand.
- Complex 2, upon heating, undergoes C-Br oxidative addition to form complex 3.
- Kinetic studies indicate a unimolecular reaction pathway without ligand dissociation.
- DFT studies suggest a mechanism involving platinum "walking" along the pi-system to the C-Br bond.
Conclusions:
- The reaction proceeds via a novel intramolecular C-Br oxidative addition mechanism.
- The platinum center's ability to migrate within the pi-system is key to the transformation.
- This study provides insights into the reactivity of platinum complexes with functionalized vinylpyridine ligands.
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