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Stabilizing Halogen-Bonded Complex between Metallic Anion and Iodide.

Fei Ying1, Xu Yuan2,3, Xinxing Zhang2,3

  • 1Key Laboratory of Cluster Science of Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China.

Molecules (Basel, Switzerland)
|November 26, 2022
PubMed
Summary
This summary is machine-generated.

Strong halogen bonds between metal anions and halides are challenging. Researchers found that using trifluoromethyl iodide (CF3I) with a protected metal anion like manganese carbonyl (Mn(CO)5-) enables stable halogen bonding.

Keywords:
halogen bondmetallic anionnucleophilic substitution reactionquantum chemistry calculationreductive elimination

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Area of Science:

  • Inorganic Chemistry
  • Supramolecular Chemistry
  • Computational Chemistry

Background:

  • Halogen bonds (XBs) involving metal anions are rare due to the high reactivity of metal anions.
  • The manganese pentacarbonyl anion, Mn(CO)5-, presents a unique structure with a protected metal core and negative charge, making it a potential XB acceptor.
  • Understanding interactions between metal anions and XB donors is crucial for designing novel chemical systems.

Purpose of the Study:

  • To investigate the feasibility of forming halogen bonds between the Mn(CO)5- anion and an iodide XB donor.
  • To explore the factors influencing the stability and formation of such halogen-bonded complexes.
  • To identify strategies for overcoming the inherent reactivity challenges of metal anions in XB interactions.

Main Methods:

  • Electrospray ionization was used to prepare the Mn(CO)5- anion in the gas phase.
  • Mass spectrometry was employed to study the reaction of Mn(CO)5- with methyl iodide (CH3I).
  • Density functional theory (DFT) calculations were performed to analyze interaction energies and reaction pathways.

Main Results:

  • The reaction of Mn(CO)5- with CH3I primarily yielded a product of nucleophilic substitution, not a stable halogen-bonded complex, due to weak I···Mn interaction.
  • DFT calculations predicted that using trifluoromethyl iodide (CF3I) instead of CH3I significantly strengthens the halogen bond.
  • CF3I also substantially increases the nucleophilic substitution barrier, stabilizing the halogen-bonded complex (XC) CF3-I···Mn(CO)5-.

Conclusions:

  • A protected metal core and an electron-withdrawing group on the halide are key to achieving strong halogen bonding with metal anions.
  • The study demonstrates a viable strategy for forming stable halogen bonds involving metallic anions, expanding the scope of XB chemistry.
  • This work opens avenues for designing new supramolecular structures and functional materials based on metal-anion halogen bonding.