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Characterization of a Lewis adduct in its inner and outer forms
Science ( IF 44.7 ) Pub Date : 2024-09-12 , DOI: 10.1126/science.adp7465
Wei-Chun Liu 1 , François P Gabbaï 1
Affiliation  

The entrance channel of bimolecular reactions sometimes involves the formation of outer complexes as weakly bound, fleeting intermediates. Here, we characterize such an outer complex in a system that models the bimolecular, C-O bond–forming reaction of a phosphine oxide Lewis base with a carbenium Lewis acid. Crystallographic studies show that the C-O distance in the outer form exceeds that of the final or inner adduct by 1.1 angstroms. As the system samples the two forms of the complex, which correspond to minima on the corresponding potential energy surface, the C-O linkage switches from a secondary interaction in the outer complex to a dative bond in the inner complex. This phenomenon is harnessed as a functional feature to stabilize xanthylium-based photoredox catalysts.

中文翻译:


路易斯加合物的内部和外部形式的特征



双分子反应的入口通道有时涉及形成弱结合、转瞬即逝的中间体的外部复合物。在这里,我们在模拟氧化膦 Lewis 碱与羧 Lewis 酸的双分子 C-O 键形成反应的系统中表征了这种外部复合物。晶体学研究表明,外部形式的 C-O 距离比最终或内部加合物的距离高出 1.1 埃。当系统对对应于相应势能表面上的最小值的络合物的两种形式进行采样时,C-O 键从外部配合物中的次级相互作用切换到内部配合物中的配格键。这种现象被用作稳定氧杂璽基光氧化还原催化剂的功能特性。
更新日期:2024-09-12
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