6533b838fe1ef96bd12a3c23
RESEARCH PRODUCT
Design of neutral Lewis superacids of group 13 elements.
Leonie Anna MückLeonie Anna MückAlexey Y. TimoshkinGernot Frenkingsubject
Boron groupchemistry.chemical_elementAcceptorBond-dissociation energyInorganic ChemistrychemistryComputational chemistryOrganic chemistryMoleculeLewis acids and basesPhysical and Theoretical ChemistryGalliumBoronBasis setdescription
A general approach toward superstrong neutral Lewis acids, featuring both the pyramidalization of acceptor molecules and the introduction of electron-withdrawing substituents, is proposed and examined theoretically. Complexes of group 13 element derivatives with ammonia at the B3LYP and MP2 levels of theory with def2-TZVPP basis set are considered as examples. Pyramidalization of the acceptor molecule significantly increases its Lewis acidity (by 50-60 kJ mol(-1) for aluminum and gallium compounds and by 120-130 kJ mol(-1) for boron compounds). An additional increase of the complex stability of 55-75 kJ mol(-1) may be achieved by fluorination. The combined increase of the bond dissociation energy amounts to 110-190 kJ mol(-1), which is equivalent to 19-33 orders of magnitude in Lewis acidity.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2011-12-16 | Inorganic chemistry |