期刊文献+

环硼氮烷与HCl,CHCl_3构成的分子间氢键的理论研究 被引量:2

Theoretical study of the hydrogen bonding between borazine and HCl,CHCl_3
下载PDF
导出
摘要 用MP2方法和B3LYP方法,在6-31G(d,p)基组下对复合物环硼氮烷—HCl体系和环硼氮烷—CHCl3体系进行优化,研究了其分子间氢键的本质。计算结果表明,氯仿与环硼氮烷分子之间的相互作用使C—H键长缩短,振动频率增大(蓝移),而HCl与环硼氮烷分子之间的相互作用使H—Cl键长增长,振动频率减小(红移)。自然键轨道(NBO)分析表明,影响氢键红移和蓝移主要有3个因素:n(Y)→σ*(X—H)超共轭作用、X—H键轨道再杂化和质子供体电子密度重排。其中,超共轭作用属于键伸长效应,电子密度重排和轨道再杂化属于键收缩效应。环硼氮烷—HCl体系的构型1和2伸长效应处于优势地位导致形成红移氢键;环硼氮烷—CHCl3体系中,由于键收缩效应处于优势地位导致形成蓝移氢键。 The geometries of borasine-HCl and borazine-CHCl3 complexes were calculated at the MP2 and B3LYP/6 -31G(d,p) levels, and the essence of the two intermolecular H - bond were researched. The results indicated that the interaction between chloroform and borazine shortened the length of the C-H bond and increased the vibration frequencies (blue - shifted ), and the interaction between HCl and borazine increased the length of the H-Cl bond and decreased the vibration frequencies (red - shifted). The NBO analysis showed that blue - shifted of the C-H bond and red - shifted of the H-Cl bond were controlled by a balance of three main factors:X-H bond lengthened by n(Y)→σ* (X-H) hypereonjugative interaction, X-H bond shortened by rehybridizative interaction and redistribution of electron density in proton donor. The elongation effect led to red - shifting H - bond in borazine-HCl system;the contractive effect in borazine-CHCl3 system led to blue -shifting H -bond.
出处 《化学研究与应用》 CAS CSCD 北大核心 2009年第6期810-816,共7页 Chemical Research and Application
基金 四川省教育厅自然科学项目预研课题(2005C017)
关键词 环硼氮烷-HCl体系 环硼氮烷-CHCl3体系 分子间氢键 自然键轨道分析 borazine-HCl system borazine-CHCl3 system intermolecular H - bond natural bond orbital analysis
  • 相关文献

参考文献27

  • 1刘焕英,胡競丹,杜浪涛,李权.3,4,5-三羟基苯甲酸二聚体氢键结构性质[J].化学研究与应用,2007,19(1):106-110. 被引量:2
  • 2李绛,谢代前,鄢国森,谢代前.呋喃与HCl和CHCl_3构成的分子间氢键的理论研究[J].中国科学(B辑),2003,33(1):21-25. 被引量:14
  • 3Karpfen A, Kryachko E S. Blue - shifted hydrogen - bonded complexes Ⅱ: CH3 F…(HF) 1≤n≤~3 and CH2 F2 … (HF)1 ≤n≤3 [ J ]. Chem. Phys. ,2005,310 ( 1-3 ) :77-84.
  • 4Rutkowski K S, Rodziewicz P, Melikova S M , et al. Blue shifted F3 CH … FCD3 and Cl3 CH … FCD3 weakly H - bound complexes: Cryospectroscopic and ab initio study [ J ]. Chem Phys,2005,313 ( 1-3 ):225-243.
  • 5McDowell S A C. Blue and red shifts in F3 C - HB ( B = FH,C1H, OH2, SH2 and C1) complexes predicted by a perturbative model [ J ]. Chem Phys Lett, 2006,424 ( 4-6 ) : 239-242.
  • 6杨颙,张为俊,裴世鑫,邵杰,黄伟,高晓明.N-H…O红移氢键和蓝移氢键的理论研究[J].中国科学(B辑),2006,36(3):218-226. 被引量:22
  • 7Feng Y,Zhao S W,Liu L,et al.. Blue -shifted dihydrogen bonds [ J ]. J Phys Org Chem,2004 ,17 : 1099-1106.
  • 8Lu P, Liu G Q, Li J C. Existing problems in theoretical determination of red - shifted or blue - shifted hydrogen bond [ J ]. J Mol Struct ( Theochem ) , 2005,723 ( 1-3 ) : 95-100.
  • 9Hobza P, Havalas Z. Improper, blue - shifting hydrogen bond[J]. Theor Chem Acc,2002,108:325-334.
  • 10Masunov A, Dannenberg J J. C - H bond - shortening upon hydrogen bond formation: Influence of an electric field[J]. J Phys Chem A ,2001,105(19) :4737-4740.

二级参考文献106

共引文献53

同被引文献5

引证文献2

相关作者

内容加载中请稍等...

相关机构

内容加载中请稍等...

相关主题

内容加载中请稍等...

浏览历史

内容加载中请稍等...
;
使用帮助 返回顶部