Iminophosphorano‐Substituted Bispyridinylidenes: Redox Potentials and Substituent Constants from Tolman Electronic Parameters,Chemistry - A European Journal

当前位置： X-MOL 学术 › Chem. Eur. J. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Iminophosphorano‐Substituted Bispyridinylidenes: Redox Potentials and Substituent Constants from Tolman Electronic Parameters
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-10-06 , DOI: 10.1002/chem.202004153
Nicholas A. Richard ₁ , Chun Keat Khor ₁ , Sydney M. Hetherington ₁ , Scott L. Mills ₁ , Andreas Decken ₁ , C. Adam Dyker ₂

Affiliation

Bispyridinylidenes (BPYs) have emerged as an important class of neutral organic electron donors, with redox potentials that vary widely with choice of substituent. Methods to predict the effect of substitution on the redox potential are therefore highly desirable. Here we show that the redox potential of BPYs featuring iminophosphorano substituents (R₃P=N‐), which represent the most reducing class of BPYs, can be predicted based on the well‐known Tolman electronic parameter (TEP) for the respective phosphine fragment (R₃P). Moreover, building on earlier work relating redox potentials to Hammett‐type substituent constants, it is now possible to quantitatively predict σ_p⁺ values for iminophosphorano substituents from TEP values. These results provide a path for precisely tailoring redox potentials of iminophosphorano‐substituted BPYs, but also give quantitative descriptors for how these highly versatile iminophosphorano substituents can impact the properties of any molecular scaffold.

中文翻译：

亚氨基磷酸基取代的双吡啶亚基：托尔曼电子参数的氧化还原电势和取代常数

双吡啶亚基（BPYs）已成为一类重要的中性有机电子给体，其氧化还原电势随取代基的选择而变化很大。因此，非常需要预测取代对氧化还原电势的影响的方法。在此我们表明，可以基于各个膦片段的众所周知的托尔曼电子参数（TEP）来预测具有亚氨基磷酸基取代基（R ₃ P = N-）的BPY的氧化还原电势，这是BPY还原性最高的一类。（R ₃ P）。此外，基于将氧化还原电势与Hammett型取代基常数相关的早期工作，现在可以定量预测_σp⁺从TEP值中获得亚氨基磷酸基的取代基这些结果提供了一条精确调整亚氨基磷酸基取代的BPY氧化还原电位的途径，同时也为这些高度通用的亚氨基磷酸基取代基如何影响任何分子支架的性能提供了定量描述。

更新日期：2020-10-06

点击分享查看原文

点击收藏

阅读更多本刊最新论文