计算和实验证据表明阴离子受体配合物中出现的平衡同位素效应。

Department of Chemistry & Biochemistry and the Materials Science Institute, University of Oregon , Eugene, Oregon 97403-1253, United States.

Department of Chemistry, Oregon State University , 153 Gilbert Hall, Corvallis, Oregon 97331, United States.

J Am Chem Soc. 2017 Mar 22;139(11):3962-3965. doi: 10.1021/jacs.7b00612. Epub 2017 Mar 10.

The measurement of a deuterium equilibrium isotope effect (EIE) for the aryl CH···Cl interaction of anion receptor 1H/1D is reported. Computations corroborate the results of solution measurements for a small, normal EIE in the full complex (K/K = 1.019 ± 0.010). Interestingly, isotope effects involving fragments of the anion receptor (urea, aryl ring, etc.) are predicted to produce an inverse effect. This points to an unusual and subtle structural organization effect of the anion receptor complex that changes the nature of the combined interactions to a normal isotope effect. The reversal of EIE values suggests that overall architecture of the anion receptor can dramatically impact the nature of bonding in these complexes.

报告了测定阴离子受体 1H/1D 的芳基 CH···Cl 相互作用的氘平衡同位素效应 (EIE)。计算结果与完整配合物中小的正常 EIE 的溶液测量结果相符 (K/K = 1.019 ± 0.010)。有趣的是，阴离子受体片段（脲、芳环等）的同位素效应预计会产生相反的影响。这表明阴离子受体配合物具有不寻常且微妙的结构组织效应，改变了组合相互作用的性质，使其成为正常的同位素效应。EIE 值的反转表明，阴离子受体的整体结构可以显著影响这些配合物中键合的性质。