Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 75, Issue 9, Pages 2971-2980Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo100195w
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Funding
- Norwegian Research Council [179568/V30]
- Deutsche Forschungsgemeinschaft
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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.
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