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Interconversion between the enantiomers of chiral five-coordinate Me3Pt(IV) complexes
1Davenport Chemical Research Laboratory, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada, M5S 3H6.
Inorganic Chemistry
|October 14, 2011
Summary
New chiral platinum(IV) complexes were synthesized from platinum(II) precursors. These complexes exhibit chirality due to interligand repulsion, with isomerization occurring via ligand twisting.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Stereochemistry
Background:
- Dinuclear platinum(II) complexes featuring 3,4-bis(quinolin-8-yl)thiophene ligands were investigated.
- These complexes serve as precursors for synthesizing novel platinum(IV) compounds.
Purpose of the Study:
- To synthesize and characterize new chiral mononuclear five-coordinate methylplatinum(IV) complexes.
- To elucidate the origin and mechanism of chirality in these platinum(IV) complexes.
Main Methods:
- Reaction of dinuclear platinum(II) complexes with methyl trifluoromethanesulfonate (MeOTf).
- Synthesis of a tetrakis[3,5-bis(trifluoromethyl)phenyl]borate salt for structural analysis.
- Variable-temperature Nuclear Magnetic Resonance (NMR) spectroscopy.
- Computational studies.
Main Results:
- Successful synthesis of chiral mononuclear five-coordinate methylplatinum(IV) complexes.
- Observed differences in symmetry between solution and solid states for the synthesized complexes.
- Chirality was attributed to interligand repulsion, not ligand asymmetry.
- Ligand-twisting isomerization identified as the pathway for enantiomer interconversion.
Conclusions:
- The study demonstrates the formation of chiral platinum(IV) complexes through a novel synthetic route.
- Interligand repulsion is confirmed as the source of chirality in these systems.
- A ligand-twisting isomerization mechanism explains the observed enantiomeric interconversion.
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