Theoretical exploration of pnicogen bond noncovalent interactions in HCHO· · · PH2X (X=CH3, H, C6H5, F, Cl, Br, and NO2) complexes

Journal of Chemical Sciences

Xiang Zhao2²  Zhao Yuan³  Kun Yuan1¹  Yuan-Cheng Zhu1¹  Yan-Zhi Liu¹ 

[1] College of Chemical Engineering and Technology, Key Laboratory for New Molecule Materials Design and Function of Gansu Universities, Tianshui Normal University, Tianshui 741001, China$$;Institute for Chemical Physics & Department of Chemistry, State Key Laboratory of Electrical Insulation and Power Equipment, Xi’an Jiaotong University, Xi’an 710049, China$$;Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, USA$$

关键词: Noncovalent interaction;    pnicogen bond;    natural bond orbital theory;    natural resonance theory;    electron density topological property.;   

DOI  :  

来源: Indian Academy of Sciences

【 摘 要 】

Pnicogen bond (ZB) is a new kind of intermolecular weak interaction, which would be an important strategy for the construction of supramolecular materials. In this paper, ab initio MP2/aug-cc-pvDZ calculations have been carried out to characterize the X-P ⋯ O ZB interactions between HCHO and PH2X (X=CH3, H, C6H5, F, Cl, Br, and NO2). The calculated interaction energies with basis set super-position error (BSSE) corrections in seven ZB complexes are between −7.51 and −20.36 kJ·mol−1. The relative stabilities of the seven complexes increase in the order: HCHO⋯ PH2CH3 < HCHO⋯ PH3 < HCHO⋯ PH2 C6H5 < HCHO⋯ PH2 Br < HCHO⋯ PH2 Cl < HCHO⋯ PH2F < HCHO⋯ PH2NO2. The natural bond orbital (NBO) and natural resonance theory (NRT) analysis were employed to investigate the electron behavior and nature of the ZBs. The natural bond orbital interactions in the ZBs are mainly LP1,2 (O) → 𝜎* (P-X). The P-X (X= Br, Cl, F and NO2) are more suitable for acting as ZB donors than the P-X (X=H, CH3 and C6H5) groups. The electron density topology properties based on atoms-inmolecules (AIM) theory showed that the ZB interactions in the HCHO⋯ PH2X (X=Br, Cl, F and NO2) are stronger than those of HCHO⋯ PH2 X(X=CH3 , H and C6H5) complexes, indicating that the electron withdrawing of X benefits for the stability of ZB structure.

【 授权许可】

Unknown