| 1 | Theoretical study of the interaction mechanism of single-electron halogen bond complexes H_3C…Br-Y(Y=H,CN,NC,CCH,C_2H_3)显示文摘The characteristics and structures of single-electron halogen bond complexes H3C…Br-Y(Y = H,CCH,CN,NC,C2H3) have been investigated by theoretical calculation methods.The geometries were optimized and frequencies calculated at the B3LYP/6-311++G level.The interaction energies were corrected for basis set superposition error(BSSE) and the wavefunctions obtained by the natural bond orbital(NBO) and atom in molecule(AIM) analyses at the MP2/6-311++G level.For each H3C…Br-Y complex,a single-electron Br bond is formed between the unpaired electron of the CH3(electron donor) radical and the Br atom of Br-Y(electron acceptor);this kind of single-electron bromine bond also possesses the character of a'three-electron bond'.Due to the formation of the single-electron Br bond,the C-H bonds of the CH3 radical bend away from the Br-Y moiety and the Br-Y bond elongates,giving red-shifted single-electron Br bond complexes.The effects of substituents,hybridization of the carbon atom,and solvent on the properties of the complexes have been investigated.The strengths of single-electron hydrogen bonds,single-electron halogen bonds and single-electron lithium bonds have been compared.In addition,the single-electron halogen bond system is discussed in the light of the first three criteria for hydrogen bonding proposed by Popelier. | LI ZhiFeng1,SHI XiaoNing1,TANG HuiAn1 & ZHANG JunYan2 1College of Life Science and Chemistry,Tianshui Normal University,Tianshui 741001,China 2Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China | 2010 | Science China Chemistry2010，53，1： | 5 |
| 2 | Weak interaction between CH_3SO and HOCl: Hydrogen bond, chlorine bond and oxygen bond显示文摘B3lyp/6-311++g** and mp2/6-311++g** calculations were used to analyze the interaction between CH3SO and HOCl. Nine (complex A: S1A-S9A) and five (complex B: S4B-S7B and S10B) minima were localized on the potential energy surface of CH3SO…HOCl complexes at b3lyp/6-311++g** and mp2/ 6-311++g** computational levels, respectively. The AIM and NBO theories were also applied to explain the nature of the complexes. Bonding energy of complexes A and B corrected with BSSE falls in the ranges of -0.4―-41.4 kJ·mol-1 and -6.9―-35.8 kJ·mol-1 at mp2/6-311++g** level, respectively. The re- sults show that a novel oxygen bond complex (S6) exists in the system, besides hydrogen bond and chlorine bond. Especially, S6B-F, S6B-Br and S7B are blue shifted complexes compared with red shifted S6A, because the electron transfer occurs between LP1(S8) and σ*(O5-Cl7), resulting in the increase of O5-Cl7 and the decrease of vibrational frequency. The complex of S10B has characteristics of both red shift and blue shift. | LI ZhiFeng LI HongYu LIU YanZhi SHI XiaoNing TANG HuiAn | 2009 | Chinese Science Bulletin2009，54，17： | 0 |
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