Anion Binding Based on Hg3 Anticrowns as Multidentate Lewis Acidic Hosts
Oliver Loveday1, Jesús Jover1, Jorge Echeverría2
1Secció de Química Inorgànica, Departament de Química Inorgànica i Orgànica and Institut de Química Teòrica i Computacional (IQTC-UB), Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain.
Inorganic Chemistry
|August 1, 2022
Summary
Perfluorinated polymercuramacrocycles exhibit specific anion binding capabilities. Computational analysis reveals orbital interactions crucial for adduct geometry and pseudo-octahedral coordination spheres in mercury complexes.
Area of Science:
- Supramolecular Chemistry
- Organometallic Chemistry
- Computational Chemistry
Background:
- Perfluorinated polymercuramacrocycles are a class of cyclic organometallic compounds.
- Understanding their anion binding properties is essential for designing novel materials and catalysts.
- Previous studies have not fully elucidated the factors governing their coordination preferences and adduct geometries.
Purpose of the Study:
- To investigate the anion binding capabilities of perfluorinated polymercuramacrocycles.
- To determine the coordination preferences of these macrocycles towards Lewis bases.
- To elucidate the electronic and structural factors influencing the formation and geometry of adducts.
Main Methods:
- Structural analysis using the Cambridge Structural Database (CSD).
- Computational analysis including interaction energy calculations and energy decomposition analysis (EDA).
- Natural resonance theory (NRT) and natural bond orbital (NBO) analyses to study orbital interactions.
Main Results:
- Identified specific coordination preferences of the macrocycles for anionic and neutral Lewis bases.
- Computed and decomposed interaction energies, revealing key contributions to binding.
- Demonstrated the critical role of involved orbitals in determining adduct geometry via NRT and NBO analyses.
Conclusions:
- The study provides a comprehensive understanding of anion binding in perfluorinated polymercuramacrocycles.
- Orbital interactions are fundamental in dictating the geometry of the resulting complexes.
- Findings generalize to explain the formation of pseudo-octahedral second coordination spheres in linear Hg(II) complexes.
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