A COMPARATIVE STUDY OF META/PARA SUBSTITUTION EFFECTS ON THE HYDROGEN-BONDED COMPLEX OF ANILINE-H2O: OBSERVATIONS FROM COMPUTATION

作者：Tan Ying; Zhu Lijuan; Xiao Xiuchan; He Shuhua; Guo Yanzhi; Wen Zhining; Li Menglong; Pu Xuemei^*; Tian Anmin

来源：Journal of Theoretical and Computational Chemistry, 2011, 10(5): 567-579.

DOI：10.1142/S0219633611006645

• Position of substituent
• aniline-H2O
• hydrogen bond
• B3LYP
• NBO

Compared with para-substitution, substituent effects (R = NH2, OH, CH3, F, Cl, H, SiH3, CHO, CN, NO2) of meta-position effects on hydrogen-bonded complex of aniline with one water molecule are studied at B3LYP/6-311++G(d, p) level of theory. The differences in hydrogen bonding and some properties associated with the H-bond (such as bond length, vibrational frequency, binding energies, pK(a) values of aniline derivatives) are discussed between meta and para substitutions. Natural bond orbital (NBO) and atoms in molecules (AIM) analysis are applied to investigate the physical origin of the differences. The results show that the differences are mainly attributed to the variations in electron delocalization from amino group to phenyl ring (reflected by n(N) -> pi*(C=C) interaction) induced by substituents.

• 出版日期2011-10
• 单位四川大学