Laboratoire de Chimie, École Normale Supérieure de Lyon CNRS, UCLB, 46 allée d'Italie, F-69364, Lyon, France.
Aix Marseille Univ, CNRS, Centrale Marseille, iSm2, Marseille, France.
Chempluschem. 2020 May;85(5):977-984. doi: 10.1002/cplu.202000204.
Proazaphosphatranes (also named Verkade's superbases) and their azaphosphatrane conjugated acids have been recently been shown to be confined in either covalent or self-assembled molecular cages, or immobilized in nanopores of hybrid materials. The encapsulation of these phosphorus moieties turns out to strongly affect both their acid-base, catalytic, and recognition properties. The thermodynamics and kinetics of the proton transfer as well as the selectivity and catalytic activities of Verkade's superbases were strongly changed upon their confinement in a hemicryptophane cavity. Moreover, self-assembled cages, including azaphosphatrane moieties, were found to display remarkable anion recognition properties in water. In this Minireview, these new aspects of the chemistry of aza- and proaza-phosphatranes are presented, in order to highlight the great potential of such an approach.
Proazaphosphatranes（也称为 Verkade 的超碱）及其氮杂膦烷共轭酸最近被证明被局限在共价或自组装的分子笼中，或固定在混合材料的纳米孔中。这些磷部分的封装事实证明强烈影响它们的酸碱、催化和识别性质。质子转移的热力学和动力学以及 Verkade 的超碱的选择性和催化活性在它们被限制在半cryptophane 腔中时发生了强烈变化。此外，包括氮杂膦烷部分的自组装笼在水中被发现具有显著的阴离子识别性质。在这篇综述中，介绍了氮杂膦烷和氮杂氮磷烷化学的这些新方面，以强调这种方法的巨大潜力。
