Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5417324 | Journal of Molecular Structure: THEOCHEM | 2009 | 7 Pages |
Abstract
The unusual and strong cation-Ï interactions are found between cations (H+, Li+, Na+, Be2+, and Mg2+) and the electron-deficient BB bond using MP2(full) and CCSD(T) methods at 6-311+G(2df) (6-311++G(2df,2p) for H+ complexes) and aug-cc-pVTZ levels, accompanied by the BB bond contraction. A comparison with those between the corresponding cations and HCCH are also carried out. The binding energies follow the order of OCBBCOâ¯H+ â OCBBCOâ¯Be2+ > OCBBCOâ¯Mg2+ >> OCBBCOâ¯Li+ > OCBBCOâ¯Na+ and OCBBCOâ¯cations > HCCHâ¯cations at four levels. The atoms in molecules (AIM) theory has been applied to convince covalent interaction in the H+ complexes and confirm that the electron-deficient BB triple bond can be as the strong Ï-electron donor in the cation-Ï interaction. The analyses of natural bond orbital (NBO) and electron density shifts have revealed the nature of the cation-Ï interaction and explained the origin of BB bond contraction.
Related Topics
Physical Sciences and Engineering
Chemistry
Physical and Theoretical Chemistry
Authors
Duan-lin Cao, Fu-de Ren, Sheng-nan Liu, Shu-sen Chen,