Rate-Determining Factors in Nucleophilic Aromatic Substitution Reactions

被引:108
作者
Fernandez, Israel [4 ]
Frenking, Gernot [3 ]
Uggerud, Einar [1 ,2 ]
机构
[1] Univ Oslo, Massespektrometrilab, N-0315 Oslo, Norway
[2] Univ Oslo, Senter Teoretisk & Beregningsbasert Kjemi CTCC, Kjemisk Inst, N-0315 Oslo, Norway
[3] Univ Marburg, Fachbereich Chem, D-35043 Marburg, Germany
[4] Univ Complutense, Fac Quim, Dept Quim Organ, E-28040 Madrid, Spain
关键词
DENSITY-FUNCTIONAL THEORY; LONE-PAIR DONORS; GAS-PHASE; MEISENHEIMER COMPLEXES; PROTON AFFINITIES; S(N)2 REACTIONS; CHEMICAL-BOND; EXCHANGE; IONS; DELOCALIZATION;
D O I
10.1021/jo100195w
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Quantum chemical calculations (OPBE/6-311++G(d,p)) have been performed to uncover the electronic factors that govern reactivity in the prototypical SNAr reaction. It was found that intrinsic nucleophilicity-expressed as the critical energy (the energy required for forming the Meisenheimer structure Ph(X)(2)(-)) in the identity substitution reaction X- + PhX X -> + X- + PhX (Ph = phenyl) shows the following approximate trend: NH2- approximate to OH- approximate to F- >> PH2- approximate to SH- approximate to Cl- > AsH2- approximate to SeH- approximate to Br-. The periodic trends are discussed in terms of molecular properties (proton affinity of X- expressing Lewis basicity of the nucleophile and C(1s) orbital energy expressing Lewis acidity of the substrate) based on a dative bonding model. Furthermore, the stepwise progress of the reactions and the critical structures are analyzed applying energy decomposition analysis. Increased stability, and thereby increased intrinsic nucleophilicity, correlates with decreasing aromatic character of the Meisenheimer structure. This apparent contradiction is explained in consistency with the other observations using the same model.
引用
收藏
页码:2971 / 2980
页数:10
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