A theoretical study on unusual intermolecular T-shaped X-H center dot center dot center dot pi interactions between the singlet state HB=BH and HF, HCl, HCN or H2C2

作者：Ren Fu de^*; Cao Duan lin; Wang Wen liang; Ren Jun; Hou Su qing; Chen Shu sen

来源：Journal of Molecular Modeling, 2009, 15(5): 515-523.

DOI：10.1007/s00894-008-0415-8

• B=B double bond
• Electron density shifts
• T-shaped X-H center dot center dot center dot pi hydrogen bond

The unusual T-shaped X-H center dot center dot center dot pi hydrogen bonds are found between the B=B double bond of the singlet state HB=BH and the acid hydrogen of HF, HCl, HCN and H2C2 using MP2 and B3LYP methods at 6-311++G(2df, 2p) and aug-cc-pVTZ levels. The binding energies follow the order of HB = BH center dot center dot center dot HF > HB = BH center dot center dot center dot HCl > HB = BH center dot center dot center dot HCN>HB=BH center dot center dot center dot H2C2. The hydrogen-bonded interactions in HB=BH center dot center dot center dot HX are found to be stronger than those in H2C=CH2 center dot center dot center dot HX and OCB=BCO center dot center dot center dot HX. The analyses of natural bond orbital (NBO) and the electron density shifts reveal that the nature of the T-shaped X-H center dot center dot center dot pi hydrogen-bonded interaction is that much of the lost density from the pi-orbital of B=B bond is shifted toward the hydrogen atom of the proton donor, leading to the electron density accumulation and the formation of the hydrogen bond. The atoms in molecules (AIM) theory have also been applied to characterize bond critical points and confirm that the B=B double bond can be a potential proton acceptor.

• 出版日期2009-5
• 单位中北大学; 陕西师范大学; 北京理工大学