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Fluorinated B-phenylated scorpionates as tunable platforms for stabilizing thallium(I) and silver(I)-ethylene
Anurag Noonikara-Poyil1, Vo Quang Huy Phan1, Mukundam Vanga1
1Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019, USA. dias@uta.edu.
Dalton Transactions (Cambridge, England : 2003)
|December 8, 2025
Summary
Fluorinated ligands with electron-withdrawing groups enhance stability and steric protection in thallium and silver complexes. These complexes show unique bonding and catalytic activity in alkane C-H functionalization.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Catalysis
Background:
- Bis(pyrazolyl)borate and bis(pyridyl)borate ligands are versatile scaffolds in coordination chemistry.
- Fluorinated substituents can impart unique electronic and steric properties to ligands.
- Coinage metals like silver(I) readily form complexes with π-systems such as ethylene.
Purpose of the Study:
- To synthesize and characterize thallium(I) and silver(I) complexes featuring novel fluorinated and B-phenylated bis(pyrazolyl)borate and bis(pyridyl)borate ligands.
- To investigate the influence of electron-withdrawing fluorinated groups on metal-ligand bonding and complex stability.
- To explore the catalytic applications of these silver complexes in alkane C-H functionalization.
Main Methods:
- Synthesis of fluorinated N-heterocyclic ligands and their corresponding thallium(I) and silver(I) complexes.
- Spectroscopic characterization including Nuclear Magnetic Resonance (NMR) spectroscopy (19F, 1H, 13C).
- Computational analysis using buried-volume calculations to assess steric effects.
Main Results:
- Thallium(I) complexes exhibited κ2-N,N binding and Tl-F coupling in 19F NMR, indicating proximity of fluorinated groups.
- Trigonal-planar silver(I)-ethylene complexes showed upfield NMR shifts for ethylene resonances, suggesting π-complexation.
- Buried-volume calculations quantified the steric impact of the fluorinated ligands.
- Silver complexes demonstrated catalytic activity in C-H activation of alkanes via carbene insertion.
Conclusions:
- Fluorinated groups and N-heterocyclic donors significantly influence metal-ligand interactions and the stability of coinage-metal π-complexes.
- The steric and electronic properties of these ligands are crucial for controlling reactivity.
- These findings provide insights into designing ligands for efficient and selective alkane C-H functionalization catalysis.
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